Improved coated separators, lithium batteries, and related methods

ABSTRACT

New and/or improved coatings, layers or treatments for porous substrates, including battery separators or separator membranes, and/or coated or treated porous substrates, including coated battery separators, and/or batteries or cells including such coatings or coated separators, and/or related methods including methods of manufacture and/or of use thereof are disclosed. Also, new or improved coatings for porous substrates, including battery separators, which comprise at least a matrix material or a polymeric binder, and heat-resistant particles with additional additives, materials or components, and/or to new or improved coated or treated porous substrates, including battery separators, where the coating comprises at least a matrix material or a polymeric binder, and heat-resistant particles with additional additives, materials or components are disclosed. Further, new or improved coatings for porous substrates, including battery separators, and new and/or improved coated porous substrates, including battery separators, new or improved coatings for porous substrates, including battery separators, which comprise at least (i) a matrix material or a polymeric binder, (ii) heat-resistant particles, and (iii) at least one component selected from the group consisting of a cross-linker, a low-temperature shutdown agent, an adhesion agent, and a thickener, and new and/or improved coated porous substrates, including battery separators, where the coating comprises at least (i) a matrix material or a polymeric binder, (ii) heat-resistant particles, and (iii) at least one component selected from the group consisting of a cross-linker, a low-temperature shutdown agent, an adhesion agent, a thickener, a friction-reducing agent, and a high-temperature shutdown agent are disclosed.

This application is a 371 Application to PCT/US2017/043266, filed Jul.21, 2017, which claims the benefit of and priority to U.S. ProvisionalPatent Application 62/620,087, which was filed on Jan. 22, 2018, and ishereby fully incorporated by reference herein.

FIELD

This application is directed to new and/or improved coatings for poroussubstrates, including battery separators or separator membranes, and/orcoated porous substrates, including coated battery separators, and/orbatteries or cells including such coatings or coated separators, and/orrelated methods including methods of manufacture and/or of use thereof.In accordance with at least particular embodiments, this application isdirected to new or improved coatings for porous substrates, includingbattery separators, which comprise at least a polymeric binder andheat-resistant particles with or without additional additives, materialsor components, and/or to new or improved coated porous substrates,including battery separators, where the coating comprises at least apolymeric binder and heat-resistant particles with or without additionaladditives, materials or components. In accordance with at least certainembodiments, this application is directed to new or improved coatingsfor porous substrates, including battery separators, and new and/orimproved coated porous substrates, including battery separators, andmore particularly, to new or improved coatings for porous substrates,including battery separators, which comprise at least (i) a polymericbinder, (ii) heat-resistant particles, and (iii) at least one componentselected from the group consisting of a cross-linker, a low-temperatureshutdown agent, an adhesion agent, and/or a thickener, and/or to newand/or improved coated porous substrates, including battery separators,where the coating comprises at least (i) a polymeric binder, (ii)heat-resistant particles, and (iii) at least one component selected fromthe group consisting of a cross-linker, a low-temperature shutdownagent, an adhesion agent, a thickener, a friction-reducing agent, and/ora high-temperature shutdown agent. In accordance with at least certainselected embodiments, this application is directed to new or improvedcoatings for porous substrates, including battery separators, capacitorseparators, fuel cell membranes, textile materials, garment materials orlayers, filtration materials, and the like, and new and/or improvedcoated or treated porous substrates, including battery separators, andmore particularly, to new or improved coatings for porous substrates,including battery separators, capacitor separators, fuel cell membranes,textile materials, garment materials or layers, filtration materials,and the like which comprise at least (i) a polymeric binder, (ii)optional organic and/or inorganic compression resistant, dendriteresistant, and/or heat-resistant particles, and (iii) at least onecomponent selected from the group consisting of a cross-linker, ashutdown agent, a low-temperature shutdown agent, a high temperatureshutdown agent, an adhesion agent, an X-Ray detectable element, afriction-reducing agent, and/or a thickener, and/or to new and/orimproved coated porous substrates, including battery separators, wherethe coating comprises at least (i) a polymeric binder, (ii) optionalorganic and/or inorganic compression resistant, dendrite resistant,and/or heat-resistant particles, and (iii) at least one componentselected from the group consisting of a cross-linker, a shutdown agent,a low-temperature shutdown agent, a high temperature shutdown agent, anadhesion agent, an X-Ray detectable element, a friction-reducing agent,and/or a thickener.

BACKGROUND

As technological demands increase, demands on separator performance,quality, and manufacture also increase. Various techniques have beendeveloped to improve the performance properties of membranes or poroussubstrates used as separators in lithium batteries.

Applications of polymeric coatings and ceramic-containing polymericcoatings are known methods to improve the thermal safety performance ofa microporous battery separator membrane in a lithium battery. Suchcoatings may be applied as a coating or a layer onto one or both sidesof a microporous battery separator membrane in order to promotehigh-temperature stability, control oxidation at the separator-cathodeinterface of the microporous battery separator membrane, and improvesafety performance of the microporous battery separator membrane invarious battery systems, such as lithium ion rechargeable (or secondary)battery systems. U.S. Pat. No. 6,432,586, which is incorporated hereinby reference in its entirety, discloses various ceramic-coatedseparators. Additionally, U.S. Patent Publication No. 2014/0045033,which is also incorporated herein by reference in its entirety,discloses various ceramic particle-containing polymeric coatings formicroporous battery separator membranes which may provide improvement insafety, battery cycle life, and high temperature performance. Suchcoatings may include one or more polymeric binders, one or more types ofinorganic ceramic particles and an aqueous solvent, a non-aqueoussolvent, or water. Such coatings may be applied using varioustechnologies such as, but not limited to, dip coating, knife, gravure,curtain, spray, etc. Furthermore, various known ceramicparticle-containing polymeric coatings may be applied at varyingthicknesses, such as a thickness of, for example, 2 to 6 microns ontoone or both sides of a microporous battery separator membrane.

Increasing performance standards, safety standards, manufacturingdemands, and/or environmental concerns make development of new and/orimproved coating compositions for battery separators desirable.

One possible major safety issue for lithium-ion batteries is thermalrunaway. Abuse conditions, such as overcharge, over-discharge, andinternal short-circuits, for example, can lead to battery temperaturesfar above those which the temperatures that battery manufacturersintended their batteries to be used. Shutdown of the battery, e.g., astopping of ionic flow across the separator, e.g., between an anode anda cathode in the event of thermal runaway, is a safety mechanism used toprevent thermal runaway. Certain separators in lithium-ion batteriesoffer the ability to shutdown at temperatures at least slightly lowerthan that at which thermal runaway occurs, while still retaining theirmechanical properties. Faster shutdown at lower temperatures and for alonger duration, e.g., so that the user or device has longer time toturn off the system, is very desirable.

Another possible major safety issue for lithium-ion batteries are shorts(hard or soft) caused when the electrodes contact each other. A hardshort may occur if the electrodes come into direct contact with eachother and may also occur when a lot of (maybe 100) or very large lithiumdendrites, growing from the anode, come into contact with the cathode.The result may be thermal runaway. A soft short may occur when small ora single (or a small number, like 5) lithium dendrite growing from theanode comes into contact with the cathode. Soft shorts may reduce thecycling efficiency of the battery. Certain past ceramic-coatedseparators may be good at preventing hard or soft shorts, but there is aconstant desire to improve the safety and performance or dendriteblocking function of separators. For example, it is desirable tomaintain this function with thinner and thinner membranes and coatings.

Hence, there is a need for improvements in at least the performance,safety, structure, coating, manufacture, etc. of at least certain pastseparators, membranes, coating compositions, and/or coated batteryseparators.

SUMMARY

In accordance with at least selected embodiments, this application,disclosure or inventions herein, provided or covered hereby may addressthe prior issues, needs or problems, and/or may provide or is or aredirected to new and/or improved coatings for porous substrates,including battery separators or separator membranes, and/or coatedporous substrates, including coated battery separators, and/or batteriesor cells including such coatings or coated separators, and/or relatedmethods including methods of manufacture and/or of use thereof. Inaccordance with at least particular embodiments, this application,disclosure or inventions herein or covered hereby is or are directed tonew or improved coatings for porous substrates, including batteryseparators, which comprise at least a polymeric binder andheat-resistant particles with or without additional additives, materialsor components, and/or to new or improved coated porous substrates,including battery separators, where the coating comprises at least apolymeric binder and heat-resistant particles with or without additionaladditives, materials or components. In accordance with at least certainembodiments, this application is directed to new or improved coatingsfor porous substrates, including battery separators, and new and/orimproved coated or treated porous substrates, including batteryseparators, and more particularly, to new or improved coatings forporous substrates, including battery separators, which comprise at least(i) a polymeric binder, (ii) heat-resistant particles, and (iii) atleast one component selected from the group consisting of across-linker, a low-temperature shutdown agent, an adhesion agent, and athickener, and/or to new and/or improved coated porous substrates,including battery separators, where the coating comprises at least (i) apolymeric binder, (ii) heat-resistant particles, and (iii) at least onecomponent selected from the group consisting of a cross-linker, alow-temperature shutdown agent, an adhesion agent, a thickener, afriction-reducing agent, a high-temperature shutdown agent.

In accordance with at least certain selected embodiments, this inventionor application is directed to or provides new or improved coatings forporous substrates, including battery separators, capacitor separators,fuel cell membranes, textile materials, garment materials or layers,filtration materials, and the like, and new and/or improved coated ortreated porous substrates, including battery separators, and moreparticularly, to new or improved coatings for porous substrates,including battery separators, capacitor separators, fuel cell membranes,textile materials, garment materials or layers, filtration materials,and the like which comprise at least (i) a polymeric binder, (ii)optional organic and/or inorganic compression resistant, dendriteresistant, and/or heat-resistant particles, and (iii) at least onecomponent selected from the group consisting of a cross-linker, ashutdown agent, a low-temperature shutdown agent, a high temperatureshutdown agent, an adhesion agent, an X-Ray detectable element, afriction-reducing agent, and/or a thickener, and/or to new and/orimproved coated porous substrates, including battery separators, wherethe coating comprises at least (i) a polymeric binder, (ii) optionalorganic and/or inorganic compression resistant, dendrite resistant,and/or heat-resistant particles, and (iii) at least one componentselected from the group consisting of a cross-linker, a shutdown agent,a low-temperature shutdown agent, a high temperature shutdown agent, anadhesion agent, an X-Ray detectable element, a friction-reducing agent,and/or a thickener.

In one aspect, a coating composition, e.g., a coating composition foruse on at least one side of a porous or microporous substrate ormembrane such as a battery separator, capacitor separator, fuel cellmembrane, textile material, garment material or layer, filtrationmaterial, and/or the like is described herein. The coating may also besuitable for other purposes where its properties, which are discussed infurther detail below with respect to its application to batteryseparators, would make it a suitable coating option. The coatingcomposition comprises: (i) a polymeric binder, (ii) heat-resistantparticles, and (iii) at least one additional component selected from thegroup consisting of (a) a cross-linker, (b) a low-temperature shutdownagent, (c) an adhesion agent, (d) a thickener, (e) a friction-reducingagent, and (f) a high-temperature shutdown agent. In some embodiments,the binder further comprises water as the only solvent, an aqueoussolvent, or a non-aqueous solvent. In some embodiments, the coatingcompositions may also comprise at least one selected from the groupconsisting of surfactants, antioxidants, fillers, colorants, stabilizingagents, de-foaming agents, de-bubbling agents, thickeners, emulsifiers,pH buffers, emulsification agents, surfactants, anti-settling agents,levelers, rheology modifiers, and wetting agents.

In another aspect, a separator, e.g., for a battery, such as a lithiumbattery, secondary lithium battery, lithium ion battery, secondarylithium ion battery, or the like, that comprises a porous substrate anda coating layer formed on at least one surface thereof is described. Thecoating composition comprises the coating composition described herein.In some embodiments, the coating layer is an outermost coating layer,and in other embodiments, a different coating layer is formed over or ontop of the coating layer, and in this case, the different coating layeris the outermost layer or may have yet another different coating layerformed over or on top of it. In some embodiments the coating layercomprising the coating composition described herein is coated on twosurfaces of, e.g., two opposing surfaces of, the porous substrate.

In a further aspect, a composite comprising a the separator describedherein, in direct contact with an electrode for a lithium ion battery, asecondary lithium ion battery comprising the separator described herein,and/or a device or vehicle comprising the separator described herein ora secondary lithium ion battery comprising the separator describedherein are described. The secondary lithium ion battery exhibits atleast improved safety and performance.

DRAWINGS

There may be provided duplicative color version and black and whiteversion of certain figures.

FIG. 1 is a structure description of a co-polymer or block-copolymerwhere X is a group capable of creating cross-linking between at leasttwo co-polymers or block co-polymers chains, e.g., an epoxide or alkylamine-containing group, and one embodiment of the co-polymer blockco-polymer is derived from a lactam.

FIG. 2 is a schematic representation of an example of cross-linkingbetween at least two co-polymers or block co-polymers chains created bythe co-polymer block co-polymer derived from a lactam in FIG. 1 and thepolymer chains are PVP chains so R₁, R₂, R₃, R₄, and R₅ in FIG. 1 arehydrogen and Y is 2.

FIG. 3 is a schematic diagram of selected coverage of the heat-resistantparticles by the polymeric binder. For example, when the ratio ofheat-resistant particles to polymeric binder is lower, there will bemore coverage of the heat-resistant particles with binder (e.g., asshown on the right in FIG. 3), and when the ratio of heat-resistantparticles to polymeric binder is higher, there will be less coverage ofthe heat-resistant particles, e.g., as shown on the left in FIG. 3).

FIG. 4 is schematic cross-section illustrations of respective one sidecoated (OSC) and two side coated (TSC) embodiments of inventive coatedsubstrates or coated separators.

FIG. 5 is a graphical representation of one example of shutdownperformance with resistance on one axis and temperature on the otheraxis.

FIG. 6 is a schematic graphical representation of the shutdown window ofrespective uncoated and one side coated substrates. The coated substratehas an extended shutdown window.

FIG. 7 is a schematic illustration of a lithium battery.

FIG. 8 is a graphical representation of shutdown performance ofrespective Comparative and Inventive examples.

FIG. 9 is a graphical representation of extended shutdown performance ofan Inventive example as compared to a Comparative example.

FIGS. 10A, 10B and 10C are each graphical representations of shutdownperformance of respective uncoated and coated PP/PE/PP and PE/PP/PEsubstrates.

FIG. 11 is a photographic image showing increased adhesion of thecoating layer to an electrode, e.g., an anode, by addition of anadhesion agent to the coating composition.

FIG. 12 is a photographic image showing the results of a hot tip holepropagation study. The hot tip test measures the dimensional stabilityof the separators under point heating condition. The test involvescontacting the separators with a hot soldering iron tip and measuringthe resulting hole. Smaller holes are more desirable.

FIG. 13 is a schematic cross-section illustration of an exemplaryceramic coated separator.

FIG. 14 is a sectional view of a cylindrical lithium battery, such as alithium ion battery or lithium metal battery.

DETAILED DESCRIPTION

In accordance with at least selected embodiments, aspects, or objects,this application, the disclosure or inventions herein, provides, covers,and/or addresses the prior issues, needs or problems, and/or may provideor is or are directed to new and/or improved coatings or treatments forporous substrates, including battery separators or separator membranes,and/or coated or treated porous substrates, including coated batteryseparators, and/or batteries or cells including such coatings or coatedseparators, and/or related methods including methods of manufactureand/or of use thereof. In accordance with at least particularembodiments, this application, disclosure or inventions herein orcovered hereby is or are directed to new or improved coatings for poroussubstrates, including battery separators, which comprise at least apolymeric binder and heat-resistant particles with or without additionaladditives, materials or components, and/or to new or improved coatedporous substrates, including battery separators, where the coatingcomprises at least a polymeric binder and heat-resistant particles withor without additional additives, materials or components. In accordancewith at least certain embodiments, this application is directed to newor improved coatings for porous substrates, including batteryseparators, and new and/or improved coated or treated porous substrates,including battery separators, and more particularly, to new or improvedcoatings for porous substrates, including battery separators, whichcomprise at least (i) a polymeric binder, (ii) heat-resistant particles,and (iii) at least one component selected from the group consisting of across-linker, a low-temperature shutdown agent, an adhesion agent, and athickener, and/or to new and/or improved coated porous substrates,including battery separators, where the coating comprises at least (i) apolymeric binder, (ii) heat-resistant particles, and (iii) at least onecomponent selected from the group consisting of a cross-linker, alow-temperature shutdown agent, an adhesion agent, a thickener, afriction-reducing agent, and a high-temperature shutdown agent.

In accordance with at least certain selected embodiments, this inventionor application is directed to or provides new or improved coatings forporous substrates, including battery separators, capacitor separators,fuel cell membranes, textile materials, garment materials or layers,filtration materials, and the like, and new and/or improved coated ortreated porous substrates, including battery separators, and moreparticularly, to new or improved coatings for porous substrates,including battery separators, capacitor separators, fuel cell membranes,textile materials, garment materials or layers, filtration materials,and the like which comprise at least (i) a polymeric binder, (ii)optional organic and/or inorganic compression resistant, dendriteresistant, and/or heat-resistant particles, and (iii) at least onecomponent selected from the group consisting of a cross-linker, ashutdown agent, a low-temperature shutdown agent, a high temperatureshutdown agent, an adhesion agent, an X-Ray detectable element, afriction-reducing agent, and/or a thickener, and/or to new and/orimproved coated porous substrates, including battery separators, wherethe coating comprises at least (i) a polymeric binder, (ii) optionalorganic and/or inorganic compression resistant, dendrite resistant,and/or heat-resistant particles, and (iii) at least one componentselected from the group consisting of a cross-linker, a shutdown agent,a low-temperature shutdown agent, a high temperature shutdown agent, anadhesion agent, an X-Ray detectable element, a friction-reducing agent,and/or a thickener.

In accordance with at least selected aspects, objects or embodiments ofthe present disclosure or invention, see for example, Examples (1) to(7) and Tables 1 to 4 below, such aspect, object or embodiment is or aredescribed in more detail as follows:

Compositions

In accordance with at least one aspect, object or embodiment, a coatingcomposition described herein comprises, consists of, or consistsessentially of the following: (1) a polymeric binder, optionallycomprising water as the only solvent, an aqueous solvent, or anon-aqueous solvent; (2) heat-resistant and/or compression resistantparticles; and (3) at least one additional component selected from thegroup consisting of: (a) a cross-linker, (b) a low-temperature shutdownagent, (c) an adhesion agent, (d) a thickener, (e) a friction-reducingagent., and (f) a high-temperature shutdown agent.

In some embodiments, the coating composition comprises at least twoadditional of these additional components, e.g., (a) and (d), (b) and(c), (c) and (e), or (d) and (f) in some embodiments the coatingcomposition comprises at least three of these additional components,e.g., (a), (b), and (d), (a), (c), and (d), or (c), (e), and (f), and inother embodiments the coating composition comprises one of each of theseadditional components, e.g., (a), (b), (c), (d), (e), and (f). In someembodiments, the coating composition can comprise two component (a) s,e.g., two cross-linkers, and one of component (b). Alternatively, thecoating composition can comprise three component (c) s, e.g., threeadhesion agents, and one of component (d). In some coating compositions,a single added component can, for example, act as the adhesion agent andthe low-temperature shutdown agent, and in other embodiments, theadhesion agent and the low-temperature shutdown agent are differentcompounds. The coating composition can comprise any possible combinationof additional components (a), (b), (c), (d), (e), and (f).

(1) Polymeric Binder

The polymeric binder comprises, consists of, or consists essentially ofat least one of a polymeric, oligomeric, or elastomeric material and thesame are not so limited. Any polymeric, oligomeric, or elastomericmaterial not inconsistent with this disclosure may be used. The bindermay be ionically conductive, semi-conductive, or non-conductive. Anygel-forming polymer suggested for use in lithium polymer batteries or insolid electrolyte batteries may be used. For example, the polymericbinder may comprise at least one, or two, or three, etc. selected from apolylactam polymer, polyvinyl alcohol (PVA), Polyacrylic acid (PAA),Polyvinyl acetate (PVAc), carboxymethyl cellulose (CMC), an isobutylenepolymer, an acrylic resin, latex, an aramid, or any combination of thesematerials.

In some preferred embodiments, the polymeric binder comprises, consistsof, or consists essentially of a polylactam polymer, which is ahomopolymer, co-polymer, block polymer, or block co-polymer derived froma lactam. In some embodiments, the polymeric material comprises ahomopolymer, co-polymer, block polymer, or block co-polymer according to

wherein R₁, R₂, R₃, and R₄ can be alkyl or aromatic substituents and R₅can be an alkyl substituent, an aryl substituent, or a substituentcomprising a fused ring; and wherein the preferred polylactam can be ahomopolymer or a co-polymer where co-polymeric group X can be derivedfrom a vinyl, a substituted or un-substituted alkyl vinyl, a vinylalcohol, vinyl acetate, an acrylic acid, an alkyl acrylate, anacrylonitrile, a maleic anhydride, a maleic imide, a styrene, apolyvinylpyrrolidone (PVP), a polyvinylvalerolactam, apolyvinylcaprolactam (PVCap), polyamide, or a polyimide; wherein m canbe an integer between 1 and 10, preferably between 2 and 4, and whereinthe ratio of 1 to n is such that 0≤1:n≤10 or 0≤1:n≤1. In some preferredembodiments, the homopolymer, co-polymer, block polymer, or blockco-polymer derived from a lactam is at least one, at least two, or atleast three, selected from the group consisting of polyvinylpyrrolidone(PVP), polyvinylcaprolactam (PVCap), and polyvinyl-valerolactam.

In a preferred embodiment, a co-polymer block co-polymer derived from alactam comprises, in its backbone, a group capable of creatingcross-linking between at least two co-polymers or block co-polymerschains. For example, the group may be an epoxide group or an alkylamine. When the group capable of creating cross-linking between at leasttwo co-polymers or block co-polymers chains is an epoxide, the epoxideundergoes an epoxidation reaction to create the cross-linking. In someembodiments, addition of a catalyst is required. For example, if thegroup capable of creating cross-linking between at least two co-polymersor block co-polymers chains is an epoxide, catalyst comprising an alkylamine group may be added, and if the group is an alkyl amine, a catalystcomprising an epoxide group may be added. A co-polymer orblock-copolymer described in this paragraph may have a structure asshown in FIG. 1), where X is a group capable of creating cross-linkingbetween at least two co-polymers or block co-polymers chains, e.g., anepoxide or alkyl amine-containing group. One embodiment of theco-polymer block co-polymer derived from a lactam described in thisparagraph is shown in FIG. 1.

An example of cross-linking between at least two co-polymers or blockco-polymers chains created by the co-polymer block co-polymer derivedfrom a lactam in FIG. 1 is shown in FIG. 2.

In one embodiment, the polymeric coating may comprise a polylactam ofFormula (1):

wherein R₁, R₂, R₃, and R₄ can be alkyl or aromatic substituents and R₅can be alkyl, aryl, or fused ring; andwherein the preferred polylactam can be a homopolymer or a co-polymerwhereco-polymeric group X can be a derived from vinyl, a substituted orun-substituted alkylvinyl, vinyl alcohol, vinyl acetate, acrylic acid,alkyl acrylate, acrylonitrile, maleic anhydride, maleic imide, styrene,polyvinylpyrrolidone (PVP), polyvinylvalerolactam, polyvinylcaprolactam(PVCap), polyamide, or polyimide;wherein m can be an integer between 1 and 10, preferably between 2 and4, and wherein the ratio of I to n is such that 0≤1:n≤10 or 0≤1:n≤1.

In one embodiment, the polymeric coating may comprise a polylactamaccording to Formula (2) and a catalyst:

wherein R¹, R², R³, and R⁴ can be alkyl or aromatic substituents;R⁵ can be alkyl, aryl, or fused ring;m can be an integer between 1 and 10, preferably between 2 and 4,and wherein the ratio of I to n is such that 0≤I:n≤10 or 0≤I:n≤1.and X is an epoxide or an alkyl amine.

In FIG. 2 the polymer chains are PVP chains so R₁, R₂, R₃, R₄, and R₅ inFIG. 1 are hydrogen and Y is 2. Use of a co-polymer or block co-polymerderived from a lactam that comprises, in its backbone, a group capableof creating cross-linking between at least two co-polymers or blockco-polymers chain can increase thermal stability, increase electrolytestability, improve wetting, and CV performance of a resulting coatinglayer.

In another preferred embodiment, the polymeric binder comprises,consists of, or consists essentially of polyvinyl alcohol (PVA). Use ofPVA may result in a low curl coating layer, which helps the substrate towhich is it applied stay stable and flat, e.g., helps prevent thesubstrate from curling. PVA may be added in combination with any otherpolymeric, oligomeric, or elastomeric material described herein,particularly if low curling is desired.

In another preferred embodiment, the polymeric binder may comprise,consist of, or consists essentially of an acrylic resin. The type ofacrylic resin is not particularly limited, and may be any acrylic resinthat would not be contrary to the goals stated herein, e.g., providing anew and improved coating composition that may, for example, be used tomake battery separators having improved safety. For example, the acrylicresin may be at least one, or two, or three, or four selected from thegroup consisting of polyacrylic acid (PAA), polymethylmethacrylate(PMMA), polyacrylonitrile (PAN), polymethyl acrylate (PMA).

In other preferred embodiments, the polymeric binder may comprise,consist of, or consist essentially of carboxymethyl cellulose (CMC), anisobutylene polymer, latex, or any combination these. These may be addedalone or together with any other suitable oligomeric, polymeric, orelastomeric material.

In some embodiments, the polymeric binder may comprise a solvent that iswater only, an aqueous or water-based solvent, and/or a non-aqueoussolvent. When the solvent is water, in some embodiments, no othersolvent is present. The aqueous or water-based solvent may comprise amajority (more than 50%) water, more than 60% water, more than 70%water, more than 80% water, more than 90% water, more than 95% water, ormore than 99%, but less than 100% water. The aqueous or water-basedsolvent may comprise, in addition to water, a polar or non-polar organicsolvent. The non-aqueous solvent is not limited and may be any polar ornon-polar organic solvent compatible with the goals expressed in thisapplication. In some embodiments, the polymeric binder comprises onlytrace amounts of solvent, and in other embodiments it comprises 50% ormore solvent, sometimes 60% or more, sometimes 70% or more, sometimes80% or more, etc.

The ratio of heat-resistant particles to polymeric binder in the coatingcomposition is, in some embodiments, 50:50 to 99:1, in otherembodiments, it is 70:30 to 99:1 or 90:1 to 98:2, and in furtherembodiments, it is 90:10 to 99:1. This ratio affects coverage of theheat-resistant particles by the polymeric binder. For example, when theratio of heat-resistant particles to polymeric binder is lower, therewill be more coverage of the heat-resistant particles with binder (e.g.,as shown on the right in FIG. 3), and with the ratio of heat-resistantparticles to polymeric binder is higher, there will be less coverage ofthe heat-resistant particles, e.g., as shown on the left in FIG. 3).

In a preferred embodiment, at least one of the heat-resistant particlesis coated or partially-coated by the polymeric binder. For example, insome embodiments, 0.01 to 99.99% of the surface area of at least one ofthe heat-resistant particles (or of the surface area of all of theheat-resistant particles) is coated by the binder. In some embodiments,0.01 to 99.99% of the total surface area of the heat-resistant particlesin the composition is coated with polymeric binder.

(2) Heat-Resistant and/or Compression-Resistant Particles

In another aspect, heat-resistant particles are added to the coatingcomposition described herein. The size, shape, chemical composition,etc. of these heat-resistant particles is not so limited. Theheat-resistant particles may comprise an organic material, an inorganicmaterial, e.g., a ceramic material, or a composite material thatcomprises both an inorganic and an organic material, two or more organicmaterials, and/or two or more inorganic materials.

In some embodiments, heat-resistant means that the material that theparticles are made up of, which may include a composite material made upof two or more different materials, does not undergo substantialphysical changes, e.g., deformation, at temperatures of 200° C.Exemplary materials include aluminum oxide (Al₂O₃), silicon dioxide(SiO₂), graphite, etc.

Non-limiting examples of inorganic materials that may be used to formthe heat-resistant particles disclosed herein are as follows: ironoxides, silicon dioxide (SiO₂), aluminum oxide (Al₂O₃), boehmite (Al(O)OH), zirconium dioxide (ZrO₂), titanium dioxide (TiO₂), barium sulfate(BaSO₄), barium titanium oxide (BaTiO₃), aluminum nitride, siliconnitride, calcium fluoride, barium fluoride, zeolite, apatite, kaoline,mullite, spinel, olivine, mica, tin dioxide (SnO₂), indium tin oxide,oxides of transition metals, graphite, carbon, metal, X-Ray detectablematerials, kaolin clay, calcined clay, kaolinite, meta-stable alumina,mixtures or blends thereof, and any combinations thereof.

Non-limiting examples of organic materials that may be used to form theheat-resistant particles disclosed herein are as follows: a polyimideresin, a melamine resin, a phenol resin, a polymethyl methacrylate(PMMA) resin, a polystyrene resin, a polydivinylbenzene (PDVB) resin,carbon black, graphite, and any combination thereof.

The heat-resistant particles may be round, irregularly shaped, flakes,etc. The average particle size of the heat-resistant material rangesfrom 0.01 to 5 microns, from 0.03 to 3 microns, from 0.01 to 2 microns,etc.

As described above, in a preferred embodiment, at least one of theheat-resistant particles added to the coating composition describedherein is coated or partially-coated by the polymeric binder and/or by awax. In other embodiments, the heat-resistant particles may (in additionto or as an alternative to being coated or partially-coated by thepolymeric binder) be coated or partially coated by a compatibilizer,e.g., a material that makes the particles more miscible with thepolymeric binder. Generally, the heat-resistant particles may be coatedor uncoated in any way that would not be inconsistent with the statedgoals herein.

Not wishing to be bound by theory, oxidation or reduction reactions mayoccur during the formation stage of a lithium ion battery or duringcharging or discharging of a lithium ion battery, and these reactionsmay generate byproducts that can harm battery systems. The coatingcompositions described herein may slow down or may prevent oxidationreactions that could occur for uncoated polypropylene (PP) orpolyethylene (PE) porous substrates, e.g., battery separators.Heat-resistant particles, e.g., particles comprising aluminum oxide(Al₂O₃), are chemically inert and do not undergo oxidation with anelectrolyte. Oxidative stability improvement may be obtained by placinga coated side of the separator described herein facing or against thecathode or positive electrode.

(3) Added Components

The coating composition comprises at least one, or two, or three, etc.of (a) a cross-linker, (b) a low-temperature shutdown agent, (c) anadhesion agent, (d) a thickener, (e) a friction reducing agent, and (f)a high-temperature shutdown agent.

(a) Cross-Linker

In another aspect, at least one cross-linker may be added to the coatingcomposition. The cross-linker is not so limited, and includes anycompound capable of forming a connection between two or more polymerchains in the coating composition, so long as the compounds are nototherwise incompatible with the stated goals herein. For example, thecross-linker may be a compound having multiple reactive groups, e.g.,epoxy groups, acrylate groups, etc. For example, the cross-linker maycomprise two, three, four, five, etc. reactive groups. In someembodiments, a multi-epoxy group cross-linker, which has three or morereactive groups, is preferred.

In one preferred embodiment, the cross-linker may be part of, e.g., inthe backbone of, the polymeric, oligomeric, or elastomeric material inthe polymeric binder. For example, the cross-linker may be the epoxidegroup of the co-polymer or block co-polymer derived from a lactam asshown in FIG. 1.

The cross-linker may also be a monomeric species separate from thepolymeric, oligomeric, or elastomeric material in the polymeric binder.Some examples of cross-linkers include the following: di-functionalacrylates, tri-functional acrylates including pentaerythritoltriacrylate, multi-functional acrylates such as pentaerythritoltetraacrylate, ethyoxylated(4) pentaerythritol tetraacrylate,ditri,ethylolpropane tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, and ethoxylated dipentaerythritolhexaacrylate, diepoxides including as 1,3 butane diepoxide,Bis[(4-glycidoxy)phenyl] methane and its isomers, 1,4 butanedioldiglycidyl ether, 1,2,7,8 diepoxyoctane, diglycidyl1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidoxyaniline,triepoxides including tris(2,3-epoxypropyl)isocyanurate and tris(4-hydrocyphenyl) methane triglycidyl ether, dimethacrylates,trimethacrylates, and multifunctional methacrylates.

In some preferred embodiments, the cross-linker may be an epoxy orepoxide-group containing molecule. For example, it may be a diepoxide,triepoxide, or multi-functional epoxide. To form a cross-link betweentwo or more polymers in the coating, the cross-linker may react with anucleophilic group in the polymers. For example, a nucleophilic groupcomprising N, S, or O. For example, the nucleophilic group may be anallyl amine or an alkyl alcohol.

The cross-linker may be added in any amount not inconsistent with thestated goals herein. In some preferred embodiments the amount ofcross-linker may be added at a ppm level, e.g., up to 50,000 ppm, up to10,000 ppm, up to 5,000 ppm, etc. with respect to the total coatingcomposition.

When the cross-linker is added, in some embodiment, a cross-linkingagent or catalyst can be added, which may initiate or catalyzecross-linking of, for example, two polymer chains, via the addedcross-linker. The cross-linking agent may be sensitive to heat, light,or chemical environment (e.g., pH), e.g., the cross-linking agent orcross-linker may initiate or catalyze cross-linking of one or morepolymer chains in the coating composition in response to heating,irradiation with light, or change in pH.

When a cross-linker is added to the coating composition describedherein, the inventors of this application have found that the resultingcoating and a battery separator comprising said coating (on one or twosides thereof) exhibit many beneficial properties. These propertiesinclude lower MD and TD shrinkage even at higher temperatures, e.g., atemperature of 180° C. A coating with higher thermal stability resultswhen a cross-linker is added to the coating composition describedherein.

Shrinkage is measured by placing a test sample, e.g., a coated poroussubstrate, between two sheets of paper which are then clipped togetherto hold the sample between the papers and suspended in an oven. For the“150° C. for 1 hour” testing, a sample is placed in an oven at 150° C.for 1 hour. After the designated heating time in the oven, each samplewas removed and taped to a flat counter surface using double side stickytape to flatten and smooth out the sample for accurate length and widthmeasurement. Shrinkage is measured in the both the Machine direction(MD) and Transverse direction (TD) direction (perpendicular to the MDdirection) and is expressed as a % MD shrinkage and % TD shrinkage. Forthe “180° C. for 10 minutes” testing, the sample is placed in an oven at180° C. for 10 minutes and then tested as described above for the “150°C. for 1 hour” testing. For the “180° C. for 20 minutes” testing, thesample is placed in an oven at 180° C. for 20 minutes and then tested asdescribed above for the “150° C. for 1 hour” testing. Shrinkage may bemeasured for a one-side coated porous substrate or for a two-side coatedporous substrate.

In some preferred embodiments, a coating composition comprising across-linker will not contain an inorganic component. One benefit ofsuch an embodiment may be the ability to form a thin coating such thatthe thickness of the coated porous substrate is not thicker or notsubstantially thicker than the uncoated porous substrate. For example,the coated porous substrate may be less than 500 nm thicker, less than400 nm thicker, less than 300 nm thicker, less than 200 nm thicker, lessthan 100 nm thicker, less than 50 nm thicker, or less than 1 nm thickerthan the uncoated porous substrate. This is possible, particularly inembodiments where an inorganic component is not added, because thecoating enters into the pores of the microporous membrane. Inembodiments where an inorganic component is added, the pores may beblocked or covered or partially blocked or covered by the inorganiccomponent

(b) A Low-Temperature Shutdown Agent

In another aspect, a low-temperature shutdown agent is added to thecoating compositions described herein. The type of low-temperature agentused is not so limited as long as it is not incompatible with the statedgoals herein, e.g., providing a coating composition that can be used toproduce safer lithium ion batteries. In some embodiments, thelow-temperature shutdown agent has a melting temperature that is lowerthan that of the porous film on which the coating composition is (or ismeant to be) applied. For example, if the porous film melts around 135°C., then the low-temperature shutdown agent has a melting temperaturethat is lower than 135° C.

In some embodiments, the low-temperature shutdown agent has a meltingpoint in the range of 80° C. to 130° C., sometimes in the range of 90°C. to 120° C., sometimes in the range of 100° C. to 120° C., etc.

The low-temperature shut-down agent may be a particulate having anaverage particle size ranging from 0.1 to 5.0 microns, from 0.2 to 3.0microns, from 0.3 to 1.0 microns, etc. These particles may be coated,uncoated, or partially coated.

In some preferred embodiments, the low-temperature shut down agent maybe particles comprising wax, oligomer, polyethylene (PE), for examplelow-density PE, and/or the like. These particles may be coated,uncoated, or partially coated. For example, they may be coated withlatex and/or with a polymeric binder as disclosed herein. In someembodiments, these coated low-temperature shutdown agents may be coatedwith a high-temperature shutdown agent described in greater detailbelow.

The inventors of this application have found that using a coatingcomposition, which comprise a low-temperature shutdown agent asdescribed herein, to coat a battery separator results in a betterseparator, particularly from a safety standpoint. Without wishing to bebound by any particular theory, it is believed that this improved safetyresults from extending the shutdown window, which is discussed furtherherein, so that shutdown begins at a lower temperature when compared tothe shutdown window of an uncoated separator or a coated separatorwherein the coating layer does not comprise a low-temperature shutdownagent.

(c) An Adhesion Agent

In another aspect, an adhesion agent may be added to the coatingcompositions herein. The compound used as an adhesion agent is not solimited so long as it is not incompatible with the stated goals herein.In some embodiments, adding an adhesion agent to the coatingscompositions described herein results in coatings having higher adhesionto battery electrodes, e.g., lithium battery electrodes, comparted tocoatings formed from similar coating compositions where the adhesionagent has not been added. The adhesion agent increases the “stickiness”and/or tack of coatings formed of the coating compositions describedherein. Adhesion between the heat-resistant particles in the coating andadhesion of a coating layer formed from the coating compositionsdescribed herein to a porous substrate as described herein may also beimproved. For example, the coating-to-porous substrate adhesive strengthmay be greater than 10 N/m, greater than 12 N/m, greater than 14 N/m,greater than 16 N/m, greater than 18 N/m, or greater than 20 N/m, evenin embodiments where the porous substrate has not been pre-treated toimprove coating layer adhesion. Such pre-treatments may include coronatreatment, plasma treatment, stretching, surfactant treatment/coating,and any other surface treatments and/or coatings aimed at improvingadhesion of the substrate to a coating layer. However, use of suchpre-treatments, though not necessary to achieve excellent adhesivestrength between the porous substrate and the coating layer, is notprecluded. In some embodiments, the adhesion agent may bepolyvinylpyrrolidone (PVP) or a thermoplastic fluoropolymer such aspolyvinylidene difluoride (PVdF or PVDF).

One way adhesion of the coating layer to a battery electrode is measuredis as follows: A coated battery separator as described herein is placebetween electrodes, electrolyte is injected into the space between theelectrodes, and the electrode-coated separator composite is heat-pressedat 90° C. for 12 hrs. Following this, the composite is disassembled,e.g., the separator is separated from the electrodes, and the separatoris observed. If a lot of black material, which is electrode material, isobserved on the separator, this indicates a higher adhesion between theseparator and the electrode. Lower amounts of black material, orelectrode material, indicates lower adhesion.

In some embodiments, the adhesion agent may comprise, consist of, orconsist essentially of a “dry sticky” polymer. A “dry sticky” polymer asdescribed herein is any polymer that imparts high or low tack to thecoating. A high tack coating is harder to separate after being broughtinto contact with another surface with which a bond is formed. A lowertack coating is easier to separate and reposition after being broughtinto contact with another surface with which a bond is formed. Coatingswith tack may be beneficial for battery separators used in stacked-typeor prismatic-type battery cells. It helps prevent the separator frommoving once in its proper position in the cell. A “dry sticky” polymermay be characterized by its glass transition temperature. In someembodiments, the glass transition temperature may be less than 100° C.,and preferably less than 70° C.

In some embodiments, the adhesion agent may comprise, consist of, orconsist essentially of a “wet sticky” polymer that swells and gels innon-aqueous electrolyte. The “wet sticky” polymer as described herein isnot so limited and may be any polymer that absorbs electrolyte, swellsor grows in size when it absorbs electrolyte, and/or becomes gel-likewhen it absorbs electrolyte. The electrolyte may be any electrolytesuitable for use in a secondary battery, which may include but is notlimited to electrolytes where the solvent is DEC, PC, DMC, EC, orcombinations thereof. A wet adhesion polymer will also increase adhesionof the coating, when wet, to the anode or cathode of a secondarybattery. The wet sticky polymer may be a fluoropolymer such as PvdF orPvdF-HFP. The HFP content of the PVDF-HFP may be from 1 to 50% by weightbased on the total weight of the polymer. It also may be from 1 to 40%,from 1 to 30%, from 1 to 20%, from 1 to 15%, from 1 to 10%, or from 1 to5% by weight. In some embodiments, a wet sticky polymer may be used in acoated that is to be placed in contact with the cathode of a secondarybattery such as a lithium ion battery. In such embodiments, the side ofthe separator in contact with the anode may comprise a coatingcomprising, consisting of, or consisting essentially of CMC,styrene-butadiene rubber (SBR), or acrylic.

In some embodiments, the adhesion agent comprises, consists of, andconsists a combination of a wet sticky and dry sticky polymer.

(d) Thickener

In another aspect, a thickener may be added to the coating compositionsdescribed herein. The thickener used is not so limited and can be anythickener not inconsistent with the goals stated herein. The thickener,in some embodiments, is added to adjust the viscosity of the coatingcompositions described herein. An exemplary thickener is, for example,carboxymethyl cellulose (CMC).

(e) Friction Reducing Agent

In another aspect, a friction reducing agent may be added to the coatingcompositions described herein. The friction reducing agent is not solimited, and can be any friction reducing agent not inconsistent withthe goals stated herein. For example, in some embodiments, the additionof the friction reducing agent can result in a lowering of pin removalforce and/or lowering of the coefficient of friction when films formedfrom a coating composition that contains a friction reducing agent arecompared to films formed from a coating compositions where the frictionreducing agent is not added. In some embodiments, a coating formed froma coating composition described herein is “sticky” or adheres well to anelectrode when wet, e.g., wet with electrolyte, such as PVDF orPVDF:HFP, and has good pin removal when dry. For example, in someembodiments, the pin removal force of films formed from a coatingcomposition that contains the friction reducing agent is less than orequal to 7100 g, in some embodiments, it is less than 6500 g, in someembodiments it is less than 6000 g. In some embodiments the coefficient(static) ranging from 0.2 to 0.8, sometimes 0.3 to 0.7, sometimes 0.4 to0.6, and sometimes 0.3 to 0.5.

The pin removal properties are quantified using the following procedurethat measures the ‘pin removal force (g).’

A battery winding machine was used to wind the separator (whichcomprises, consists of, or consists essentially of a porous substratewith a coating layer applied on at least one surface thereof) around apin (or core or mandrel). The pin is a two (2) piece cylindrical mandrelwith a 0.16 inch diameter and a smooth exterior surface. Each piece hasa semicircular cross section. The separator, discussed below, is takenup on the pin. The initial force (tangential) on the separator is 0.5kgf and thereafter the separator is wound at a rate of ten (10) inchesin twenty four (24) seconds. During winding, a tension roller engagesthe separator being wound on the mandrel. The tension roller comprises a⅝″ diameter roller located on the side opposite the separator feed, a ¾″pneumatic cylinder to which 1 bar of air pressure is applied (whenengaged), and a ¼″ rod interconnecting the roller and the cylinder.

The separator consists of two (2) 30 mm (width)×10″ pieces of themembrane being tested. Five (5) of these separators are tested, theresults averaged, and the averaged value is reported. Each piece isspliced onto a separator feed roll on the winding machine with a 1″overlap. From the free end of the separator, i.e., distal the splicedend, ink marks are made at ½″ and 7″. The ½″ mark is aligned with thefar side of the pin (i.e., the side adjacent the tension roller), theseparator is engaged between the pieces of the pin, and winding is begunwith the tension roller engaged. When the 7″ mark is about ½″ from thejellyroll (separator wound on the pin), the separator is cut at thatmark, and the free end of the separator is secured to the jellyroll witha piece of adhesive tape (1″ wide, ½″ overlap). The jellyroll (i.e., pinwith separator wound thereon) is removed from the winding machine. Anacceptable jellyroll has no wrinkles and no telescoping.

The jellyroll is placed in a tensile strength tester (i.e., ChatillonModel TCD 500-MS from Chatillon Inc., Greensboro, N.C.) with a load cell(50 lbs×0.02 lb; Chatillon DFGS 50). The strain rate is 2.5 inches perminute and data from the load cell is recorded at a rate of 100 pointsper second. The peak force is reported as the pin removal force.

COF (Coefficient of friction) Static is measured according to JIS P 8147entitled “Method for Determining Coefficient of Friction of Paper andBoard.”

In some preferred embodiments, the friction reducing agent is a fattyacid salt. For example, the friction reducing agent may be a metallicstearate such as Li stearate, Ca stearate, etc. Other possible frictionreducing agents include siloxanes, silicone resins, fluororesins waxes(e.g., paraffin wax, microcrystalline wax, low-molecular weightpolyethylene, and other hydrocarbon waxes), fatty acid esters (e.g.,methyl stearate, stearyl stearate, monoglyceride stearate), aliphaticamides (e.g., stearamide, palmitamide, methylene bis stearamide), andcombinations of any of the afore-mentioned friction reducing agents.

(f) High-Temperature Shutdown Agent

According to another aspect, a high-temperature shutdown agent is addedto the coating compositions described herein. The type ofhigh-temperature agent used is not so limited as long as it is notincompatible with the stated goals herein, e.g., providing a coatingcomposition that can be used in making safer lithium ion batteries. Insome embodiments, the high-temperature shutdown agent has a meltingtemperature that is higher than that of the porous film on which thecoating composition is (or is meant to be) applied. For example, if theporous film melts around 135° C., then the high-temperature shutdownagent has a melting temperature that is higher than 135° C.

In some embodiments, the high-temperature shutdown agent has a meltingpoint in the range of 140° C. to 220° C., sometimes in the range of 150°C. to 200° C., sometimes in the range of 160° C. to 190° C., sometimesin the range of 170° C. to 180° C., etc.

The high-temperature shut-down agent may be a particulate having anaverage particle size ranging from 0.1 to 5.0 microns, from 0.2 to 3.0microns, from 0.3 to 1.0 microns, etc. These particles may be coated,uncoated, or partially coated.

In some preferred embodiments, the high-temperature shut down agent maybe particles comprising polyvinylpyrrolidone (PVP) or polyvinylidenedifluoride (PVdF). These particles may be coated, uncoated, or partiallycoated. For example, they may be coated with latex and/or with apolymeric binder as disclosed herein. In some embodiments, these coatedparticles are coated with a low-temperature shutdown agent as describedhereinabove.

The inventors of this application have found that using a coatingcomposition, which comprise a high-temperature shutdown agent asdescribed herein, to coat a battery separator results in a betterseparator, particularly from a safety standpoint. Without wishing to bebound by any particular theory, it is believed that this improved safetyresults from extending the shutdown window, which is discussed furtherherein, to a higher temperature compared to the shutdown window of anuncoated separator or a coated separator wherein the coating layer doesnot comprise a high-temperature shutdown agent.

(4) Optionally Added Components

In another aspect, one or more of the following additional componentsare optionally added: consisting of surfactants, antioxidants, fillers,colorants, stabilizing agents, de-foaming agents, de-bubbling agents,thickeners, emulsifiers, pH buffers, emulsification agents, surfactants,anti-settling agents, levelers, rheology modifiers, and wetting agents.Two or more, three or more, four or more, etc. of these optionaladditional components may also be added to the coating compositionsdescribed herein. Further, depending on the needs and the selection ofparticles or fillers, an X-Ray detectable element may also be added. Forexample, Barium Sulfate may be added or may replace a portion of theparticles or fillers. In one embodiment, up to 30% of the particles maybe replaced with an X-Ray detectable element, such as Barium Sulfate.

Separators

In another aspect, a separator comprising, consisting of, or consistingessentially of a porous substrate and a coating layer formed on at leastone surface of the porous substrate is described herein. One-sidedcoated separators and two-side coated separators according to someembodiments herein are shown in FIG. 4.

The coating layer may comprise, consist of, or consist essentially of,and/or be formed from, any one of the coating compositions describedhereinabove. The coating layer may be wet, dry, cross-linked,uncross-linked, etc. The coating may be applied over a PVD layer or aPVD layer may be applied over the coating. The coating may be appliedover aa adhesive layer or an adhesive layer may be applied over thecoating.

A new and/or improved separator as described herein may have or exhibitone or more of the following characteristics or improvements: (1)desirable level of porosity as observed by SEMs and as measured; (2)desirable Gurley numbers to show permeability; (3) desirable thickness;(4) a desired level of coalescing of the polymeric binder such that thecoating is improved relative to known coatings; (4) desirable propertiesdue to processing of the coated separator, including, but not limitedto, how the coating is mixed, how the coating is applied to thesubstrate, how the coating is dried on the substrate, if another coatingor material is applied over the coating (for example, a sticky (at leastwhen wet with electrolyte) or adhesive coating, stripes or spots areadded), and/or if the coating is (coatings, or layers are) compressed orcalendered; (5) improved thermal stability as shown, for example, bydesirable behavior in hot tip hole propagation studies; (6) reducedshrinkage when used in a lithium battery, such as a lithium ion battery;(7) improved adhesion between the heat-resistant particles in thecoating; (8) improved adhesion between the coating and the substrate;(9) improved adhesion or stick between the coated separator and one orboth electrodes of a battery; (10) improved pin removal force and/orcoefficient of friction (for example, reduced pin removal force and/orreduced coefficient of friction as compared to uncoated substrate or totypical coated materials); (11) improved wettability or wicking ofelectrolyte; and/or (12) improved oxidation resistance and/or highvoltage performance. The separator may be coated on one side (OSC), ontwo sides (TSC), have a ceramic coating (CCS) on one side (OSC CCS),have a ceramic coating (CCS) on both sides (TSC CCS), have a ceramiccoating (CCS) on one side (OSC CCS) and have a polymer or sticky coating(PCS) on the other side (OSC CCS/OSC PCS), have a ceramic coating (CCS)on both sides (TSC CCS) and have a polymer or sticky coating (PCS) ontop of one side CCS (TSC CCS/OSC PCS), have a ceramic coating (CCS) onboth sides (TSC CCS) and have a polymer or sticky coating (PCS) on topof each of the CCS (TSC CCS/TSC PCS), have CCS on top of a physicalvapor deposition (PVD), chemical vapor deposition (CVD) or atomic layerdeposition (ALD) on at least one side (collectively the depositions areVAD) (OSC VAD/OSC CCS), have CCS on top of a physical vapor deposition(PVD), chemical vapor deposition (CVD) or atomic layer deposition (ALD)on both sides (TSC VAD/TSC CCS), have PCS on top of a physical vapordeposition (PVD), chemical vapor deposition (CVD) or atomic layerdeposition (ALD) on at least one side at least one side (OSC VAD/OSCPCS), have PCS on top of a physical vapor deposition (PVD), chemicalvapor deposition (CVD) or atomic layer deposition (ALD) on both sides(TSC VAD/TSC PCS), have PCS on top of a physical vapor deposition (PVD),chemical vapor deposition (CVD) or atomic layer deposition (ALD) on oneside and have CCS on top of a physical vapor deposition (PVD), chemicalvapor deposition (CVD) or atomic layer deposition (ALD) on the otherside (TSC VAD/OSC PCS/OSC CCS), have PCS on top of the CCS, have CCS ontop of the PCS, have the VAD on top of the CCS, have the VAD on top ofthe PCS, and/or the like. The VAD can be organic and/or inorganic. TheCCS particles can be organic and/or inorganic. For example, an X-Raydetectable particle or agent can be mixed with PE particles or beads. Itmay be preferred in one embodiment to have CCS on one side and PCS onthe other side, in a second embodiment to have CCS on both sides, in athird embodiment to have PCS on both sides, in a fourth embodiment tohave CCS with PCS on top on one side and just PCS on the other side, ina fifth embodiment to have CCS with PCS on top on both sides, to have asticky CCS on both sides (the CCS includes at least one sticky componentor binder which may be the same or different on each side [the anode mayprefer one sticky material while the cathode prefers a different stickymaterial]), the separators may be pieces, leafs, sleeves, pockets,envelopes, S wrap, Z fold, sheets, rolls, flexible, rigid, and/or thelike, and/or all the separators in a battery may be of the sameconstruction or of different constructions. One battery maker may putthe CCS against the anode and the PCS or VAD against the cathode, whileanother battery maker may put the CCS against the cathode. It iscontemplated that depending on the cell type and/or on the batteryenergy and/or voltage, that the CCS, PCS or VAD may be placed againstthe anode and/or the CCS, PCS or VAD may be placed against the cathode.These objects, aspects or embodiments, and/or other related attributesof an improved coated separator are described in more detail in otherparts of this application.

The new and/or improved coated separator may have excellent quality anduniformity thus providing good manufacturing yields. The new and/orimproved coated separator may provide a battery with improved capacityand improved cycle capability. It may have fewer defects than otherknown coated separators, for example, fewer gel defects, and/or fewercrater defects. The improved and/or coated separator may have improvedcoating to porous substrate adhesion. The adhesive strength may begreater than 10 N/m, greater than 12 N/m, greater than 14 N/m, greaterthan 16 N/m, greater than 18 N/m, or greater than 20 N/m.

The new and/or improved coated porous substrate (or separator) may alsohave improved safety by exhibiting an extended shutdown window,particularly compared to the shutdown window of the porous substrateitself (e.g., the uncoated porous substrate or separator). The extendedshutdown window of the new and/or improved separator disclosed hereinmay extend between about 80° C. to about 200° C., compared to a windowof about 130° C. to 175° C. for the substrate itself. The extendedshutdown window of the new and/or improved substrate is also steady,e.g., a constant or relatively constant resistance is measured acrossthe separator over the entire window. For example, in some embodiments,the measured resistance across the separator remains above 10,000ohms/cm² over the entire window. This is considered steady. Sometimes,the measured resistance across the separator even goes as high as100,000 ohms/cm² over the extended shutdown window of the new and/orimproved separator disclosed herein. Initial shutdown of the new and/orimproved separator disclosed herein is also quick. Sometimes, duringinitial shutdown the measured resistance across the separator increasesfrom less than 10 ohms/cm² to above 10,000 ohms/cm² as the temperatureincreases between 1 to 5 degrees Celsius. For example, the resistancemight go from being 5 ohms/cm′ at 120° C. to being above 10,000 ohms/cm²at 125° C. Sometimes a temperature increase of only 4, or 3, or 2, or 1degree is necessary for this increase in resistance to occur.

Preferred thermal shutdown characteristics are lower onset or initiationtemperature, faster or more rapid shutdown speed, and a sustained,consistent, longer or extended thermal shutdown window. In a preferredembodiment, the shutdown speed is, at a minimum, 2000 ohms(Ω)·cm²/second or 2000 ohms (Ω)·cm²/degree and the resistance across theseparator increases by a minimum of two orders of magnitude at shutdown.One example of shutdown performance is shown in FIG. 5.

A shutdown window as described herein generally refers to thetime/temperature window spanning from initiation or onset of shutdown,e.g., the time/temperature at which the separator first begins to meltenough to close the pores thereof resulting in stopping or slowing ofionic flow, e.g., between an anode and a cathode, and/or increase inresistance across the separator, until a time/temperature at which theseparator begins to break down, e.g., decompose, causing ionic flow toresume and/or resistance across the separator to decrease. One exampleof an extended shutdown window as described herein is shown FIG. 6.

FIG. 6 shows that the shutdown window of a coated porous substrateaccording to embodiments described herein is extended compared to thatof the porous substrate itself, e.g., before coating with one of thecoating compositions described herein. The initiation or onset ofshutdown occurs at about 135° C. for the uncoated porous substrate andoccurs earlier after coating. Without wishing to be bound by anyparticular theory, this could result from the addition of thelow-temperature shutdown agents described herein to the coatingcompositions and/or coatings described herein. The low-temperatureshutdown agent may melt before the porous substrate, and fill orpartially fill its pores, causing an early (lower temperature)initiation of shutdown. FIG. 6 also shows that the duration of shutdownis extended from 170° C. in the uncoated porous substrate to about 190°C. after coating. Without wishing to be bound by any particular theory,this could result from the addition of a high-temperature shutdown agentas described herein to the coatings and coating compositions describedherein. The high-temperature shutdown agent may degrade at a highertemperatures than the porous substrate itself. In some embodimentdescribed herein only the shutdown initiation temperature is lowered(extending the window), in other embodiments, only the high-temperatureendpoint of the shutdown window is raised (extending the window), and insome embodiments both the upper and lower endpoints of the shutdownwindow are extended, e.g., as shown in FIG. 6.

Shutdown can be measured using Electrical Resistance testing whichmeasures the electrical resistance of the separator membrane as afunction of temperature. Electrical resistance (ER) is defined as theresistance value in ohm-cm² of a separator filled with electrolyte.Temperature may be increased during Electrical Resistance (ER) testingat a rate of 1 to 10° C. per minute. When thermal shutdown occurs in abattery separator membrane, the ER reaches a high level of resistance onthe order of approximately 1,000 to 10,000 ohm-cm². A combination of alower onset temperature of thermal shutdown and a lengthened shutdowntemperature duration increases the sustained “window” of shutdown. Awider thermal shutdown window can improve battery safety by reducing thepotential of a thermal runaway event and the possibility of a fire or anexplosion.

One exemplary method for measuring the shutdown performance of aseparator is as follows: 1) Place a few drops of electrolyte onto aseparator to saturate it, and place the separator into the test cell; 2)Make sure that a heated press is below 50° C., and if so, place the testcell between the platens and compress the platens slightly so that onlya light pressure is applied to the test cell (<50 lbs for a Carver “C”press); 3) Connect the test cell to an RLC bridge and begin recordingtemperature and resistance. When a stable baseline is attained, thenstart ramping the temperature of the heated press at 10-C/min using thetemperature controller; 4) Turn off the heated platens when the maximumtemperature is reached or when the separator impedance drops to a lowvalue; and 5) Open the platens and remove the test cell. Allow test cellto cool. Remove separator and dispose of.

(1) Porous Substrate

The porous substrate used in the separator described herein is not solimited, and may be any porous substrate that is not incompatible withthe stated goals herein. For example, the porous substrate can be anyporous substrate capable of being used as a battery separator. Theporous substrate may be a macroporous substrate, a mesoporous substrate,a microporous substrate, or a nanoporous substrate. In some preferredembodiments, the porosity of the porous substrate is from 20 to 90%,from 40 to 80%, from 50 to 70%, etc. Porosity is measured using ASTMD-2873 and is defined as the percentage of void space, e.g., pores, inan area of the porous substrate, measured in the Machine Direction (MD)and the Transverse Direction (TD) of the substrate. In some embodiments,the porous substrate has a JIS Gurley of 0.5 to 1000 seconds, in someembodiments a JIS Gurley of 100 to 800 seconds, in other embodiments theporous JIS Gurley of 200 to 700 seconds, in other embodiments it is 300to 600 seconds. Gurley is defined herein as the Japanese IndustrialStandard (JIS Gurley) and is measured herein using the OHKENpermeability tester. JIS Gurley is defined as the time in secondsrequired for 100 cc of air to pass through one square inch of film at aconstant pressure of 4.9 inches of water. In some embodiments the poresare round, e.g., a sphericity factor of 0.25 to 8.0, oblong, oroval-shaped, etc.

The material of the porous substrate is made of is not so limited. Thepolymers used in the porous substrate may be characterized asthermoplastic polymers. These polymers may be further characterized assemi-crystalline polymers. In one embodiment, semi-crystalline polymermay be a polymer having a crystallinity in the range of 20 to 80%. Suchpolymers may be selected from the following group: polyolefins,fluorocarbons, polyamides, polyesters, polyacetals (orpolyoxymethylenes), polysulfides, polyvinyl alcohols, co-polymersthereof, and combinations thereof. Polyolefins may include polyethylenes(LDPE, LLDPE, HDPE, UHMWPE), polypropylene, polybutene,polymethylpentene, co-polymers thereof, and blends thereof.Fluorocarbons may include polytetrafluoroethylene (PTFE),polychlorotrifluoroethylene (PCTFE), fluorinated ethylene propylene(FEP), ethylenechlortrifluoroethylene (ECTFE), ethylenetetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF),polyvinylfluoride (PVF), prefluoroalkoxy (PFA) resin, co-polymersthereof, and blends thereof. Polyamides may include, but are not limitedto: polyamide 6, polyamide 6/6, Nylon 10/10, polyphthalamide (PPA),co-polymers thereof, and blends thereof. Polyesters may includepolyester terephthalate (PET), polybutylene terephthalate (PBT),poly-1-4-cyclohexylenedimethylene terephthalate (PCT), polyethylenenaphthalate (PEN), and liquid crystal polymers (LCP). Polysulfidesinclude, butare not limited to, polyphenylsulfide, polyethylene sulfide,co-polymers thereof, and blends thereof. Polyvinyl alcohols include, butare not limited to, ethylenevinyl alcohol, co-polymers thereof, andblends thereof. In some embodiments the porous substrate comprises atleast one selected from the group consisting of: polyolefins (PO), e.g.,polyethylene (PE), polypropylene (PP), polymethylpentene (PMP),polyethylene terephthalate (PET), aramide, polyvinylidene fluoride(PVDF), polymer blends, polymer composites (with or without inorganicfillers Al2O3, SiO2, etc.) including polymers, co-polymers, andblock-polymers thereof, and blends, mixtures or combinations thereof.

The porous substrate may be one layer of a multi-layer membrane orseparator structure, laminate, composite, or the like. For example, theporous substrate (or coating base film) may be one layer of amulti-layer membrane or separator structure, such as a bi-layer ortri-layer membrane, of a laminate or composite, such as a polymermembrane combined with a non-woven, such as a glass and/or syntheticnon-woven, and/or the like.

The porous substrate may include other ingredients. For example, thoseingredients may include: fillers (inert particulates used to reduce thecost of the porous substrate, but otherwise having no significant impacton the manufacture of the porous substrate or its physical properties),anti-static agents, anti-blocking agents, anti-oxidants, lubricants (tofacilitate manufacture), and the like.

Various materials may be added to the polymers to modify or enhance theproperties of the porous substrate. Such materials include, but are notlimited to: (1) polyolefins or polyolefin oligomers with a meltingtemperature less than 130° C.; (2) Mineral fillers include, but are notlimited to: calcium carbonate, zinc oxide, diatomaceous earth, talc,kaolin, synthetic silica, mica, clay, boron nitride, silicon dioxide,titanium dioxide, barium sulfate, aluminum hydroxide, magnesiumhydroxide and the like, and blends thereof (3) Elastomers include, butare not limited to: ethylene-propylene (EPR), ethylene-propylene-diene(EPDM), styrene-butadiene (SBR), styrene isoprene (SIR), ethylidenenorbornene (ENB), epoxy, and polyurethane and blends thereof; (4)Wetting agents include, but are not limited to, ethoxylated alcohols,primary polymeric carboxylic acids, glycols (e.g., polypropylene glycoland polyethylene glycols), functionalized polyolefins etc; (5)Lubricants, for example, silicone, fluoropolymers, oleamide, stearamide,erucamide, calciumstearate, or other metallic stearate; (6) flameretardants for example, brominated flame retardants, ammonium phosphate,ammonium hydroxide, alumina trihydrate, and phosphate ester; (7)cross-linking or coupling agents; (8) polymer processing aid; and (9)Any types of nucleating agents including beta-nucleating agents forpolypropylene. Beta-nucleated polypropylene is disclosed in U.S. Pat.No. 6,602,593. A beta nucleator for polypropylene is a substance thatcauses the creation of beta crystals in polypropylene.)

In some embodiments, the porous substrate is a single-layer, comprisingone or more plies, a bi-layer, where each layer may comprise one or moreplies, or multi-layer porous substrate, where each layer may compriseone or more plies. When the porous substrate is a multi-layer poroussubstrate it may comprise 3 to 10 layers, 4 to 9, 5 to 8, or 6 to 7. Insome multilayer embodiments the porous substrate comprises apolypropylene (PP) layer, which comprises a majority (more than 50% ofpolymer component) PP, a polyethylene layer (PE), which comprises amajority PE, and another PP layer, which comprises a majority PP, inthat order. In other embodiments the multi-layer porous substratecomprises a PE layer, which comprises a majority of PE, a PP, whichcomprises a majority PP, and another PE layer, which comprises amajority PE, in that order. The layers comprising a majority of PP or PEmay comprise PP or PE in an amount more than 50% up to 100% of thepolymer component, respectively.

The porous substrate may be made by any one of a wet manufacturingprocess, a dry manufacturing process, a particle stretch manufacturingprocess, and a beta-nucleated biaxially-oriented (BN-BOPP) manufacturingprocess The porous substrate can be manufactured by, for example, a drystretch process (known as the Celgard® dry stretch process) of Celgard,LLC of Charlotte, N.C. The porous substrate may be any polyolefinmicroporous separator membrane available from Celgard, LLC of Charlotte,N.C. Alternatively, in other embodiments, the porous substrate may bemanufactured by a wet process, which may involve the use of solventsand/or oils, sometimes known as a phase separation or extractionprocess, of Celgard Korea, Limited of South Korea, Asahi Kasei of Japanand/or Tonen of Japan. Alternatively, in other embodiments, the poroussubstrate can be a nonwoven type membrane.

A possibly preferred porous substrate may made by a dry-stretch processand have pores of less than 2 um. A microporous substrate, for example,is a thin, pliable, polymeric sheet, foil, or film having a plurality ofpores therethrough. Such porous substrates may be used in a wide varietyof applications, including, but not limited to, mass transfer membranes,pressure regulators, filtration membranes, medical devices, separatorsfor electrochemical storage devices, membranes for use in fuel cells,and the like. The porous substrate herein is possibly most preferablymade by the dry-stretch process (also known as the CELGARD process) andmay be MD stretched, TD stretched, or MD and TD stretched (with orwithout relax)(sequential and/or simultaneous biax stretching). The drystretch process refers to a process where pore formation results fromstretching of the nonporous precursor. See, Kesting, R., SyntheticPolymeric Membranes, A structural perspective, Second Edition, JohnWiley & Sons, New York, N.Y., (1985), pages 290-297, incorporated hereinby reference. The dry-stretch process is distinguished from the wetprocess and the particle stretch process, as discussed above. Althoughnot preferred, the porous substrate may also be foamed, sintered, coldrolled, or beta nucleated biaxially oriented polypropylene (BNBOPP),and/or may have pores formed by laser, e-Beam, burning off of solvent,oil or wax components (such as in the stretching oven), dissolvedfillers or fibers, and/or the like. Also, although not preferred, theporous substrate may also be a fibrous non-woven, woven, knit, orflocked layer.

In one embodiment, the porous may be a dry-stretched porous substratehaving: 1) substantially slit, trapezoidal, or round shape pores, and 2)a ratio of machine direction tensile strength to transverse directiontensile strength in the range of 0.1 to 20, preferably 0.5 to 10.Regarding the pore shape, See, FIGS. 1-5. The round shaped pores ofFIGS. 1-3 differ from the slit shaped pores of FIGS. 4-5 and Kestin,Ibid. Further, the pore shape of the instant porous substrate may becharacterized by an aspect ratio, the ratio of the length to the widthof the pore. In one embodiment of the instant porous substrate, theround shape pore aspect ratio ranges from 0.75 to 1.25. This iscontrasted with the aspect ratio of the slit shaped pore dry-stretchedmembranes which are greater than 5.0. Regarding the ratio of machinedirection tensile strength to transverse direction tensile strength, inone round shape pore embodiment, this ratio is from 0.5 to 5.0. Thisratio differs from the corresponding ratio of the slit shape poremembranes which is greater than 10.0. Machine Direction (MD) andTransverse Direction (TD) tensile strength are measured using InstronModel 4201 according to ASTM-882 procedure. The instant porous substratemay be further characterized as follows: an average pore size in therange of 0.03 to 0.30 microns (m); a porosity in the range of 20-80%;and/or a transverse direction tensile strength of greater than 50,preferably 100, more preferably 250 Kg/cm2. The foregoing values areexemplary values and are not intended to be limiting, and accordinglyshould be viewed as merely representative of the instant poroussubstrate. Pore size is measured using the Aquapore available throughPorous Materials, Inc. (PMI). Pore size is expressed in μm.

The instant porous substrate is preferably made by a dry-stretch processwhere a precursor is MD stretched, TD stretched, biaxially stretched(i.e., not only stretched in the MD, but also in the TD direction)sequentially and/or simultaneously, may be slot die extruded (forexample, T die), may be annular die extruded (for example, bubble orparison), may be cast (like beta nucleated biaxially orientedpolypropylene, BNBOPP), may be particle stretch made, may single ormultiple layers or plies, may be co-extruded, may be laminated, may beused with other materials or layers, and/or the like. The dry-stretchprocess may also involve or include extrusion including a slight amountof pore former, oil, solvent, plasticizer, wax, oligomer, filler, orother extrusion aids (for example, a small amount of solvent, wax or oilthat may be burned off in the oven). The preferred dry-stretch processwill be discussed in greater detail below.

In general, the process for making the foregoing porous substrateincludes the steps of extruding a nonporous precursor, and then MD, TDor biaxially stretching the nonporous precursor. Optionally, thenonporous precursor may be annealed prior to stretching. In oneembodiment, the biaxial stretching includes a machine direction stretchand a transverse direction stretch with a simultaneous controlledmachine direction relax. The machine direction stretch and thetransverse direction stretch may be simultaneous or sequential. In oneembodiment, the machine direction stretch is followed by the transversedirection stretch with the simultaneous machine direction relax. Thissequential process is discussed in greater detail below.

Extrusion is generally conventional (conventional refers to conventionalfor a dry-stretch process). The extruder may have a slot die (for flatprecursor) or an annular die (for parison precursor). In the case of thelatter, an inflated parison technique may be employed (e.g., a blow upratio (BUR)). However, the birefringence of the nonporous precursor doesnot have to be as high as in the conventional dry-stretch process. Forexample, in the conventional dry-stretch process to produce a poroussubstrate with a >35% porosity from a polypropylene resin, thebirefringence of the precursor would be >0.0130; while with the instantprocess, the birefringence of the PP precursor could be as low as0.0100. In another example, a porous substrate with a >35% porosity froma polyethylene resin, the birefringence of the precursor wouldbe >0.0280; while with the instant process, the birefringence of the PEprecursor could be as low as 0.0240.

Annealing (optional) may be carried out, in one embodiment, attemperatures between Tm-80° C. and Tm-10° C. (where Tm is the melttemperature of the polymer); and in another embodiment, at temperaturesbetween Tm-50° C. and Tm-15° C. Some materials, e.g., those with highcrystallinity after extrusion, such as polybutene, may require noannealing.

Machine direction stretch may be conducted as a cold stretch or a hotstretch or both, and as a single step or multiple steps. In oneembodiment, cold stretching may be carried out at <Tm-50° C., and inanother embodiment, at <Tm-80° C. In one embodiment, hot stretching maybe carried out at <Tm-10° C. In one embodiment, total machine directionstretching may be in the range of 50-500%, and in another embodiment, inthe range of 100-300%. During machine direction stretch, the precursormay shrink in the transverse direction (conventional). Transversedirection stretching following MD stretching preferably includes asimultaneous controlled machine direction relax. This means that as theprecursor is stretched in the transverse direction the precursor issimultaneously allowed to contract (i.e., relax), in a controlledmanner, in the machine direction. The transverse direction stretchingmay be conducted as a cold step, as a hot step, or a combination ofboth. In one embodiment, total transverse direction stretching may be inthe range of 100-1200%, and in another embodiment, in the range of200-900%. In one embodiment, the controlled machine direction relax mayrange from 5-80%, and in another embodiment, in the range of 15-65%. Inone embodiment, transverse stretching may be carried out in multiplesteps. During transverse direction stretching, the precursor may or maynot be allowed to shrink in the machine direction. In an embodiment of amulti-step transverse direction stretching, the first transversedirection step may include a transverse stretch with the controlledmachine relax, followed by simultaneous transverse and machine directionstretching, and followed by transverse direction relax and no machinedirection stretch or relax. Optionally, the precursor, after machinedirection and transverse direction stretching may be subjected to a heatsetting, additional MD or TD stretching, and/or the like.

In some embodiments, the ratio of machine direction (MD) tensilestrength to transverse direction (TD) tensile strength is between 0.5 to10.0, in some embodiments 0.5 to 7.5, in some embodiments it is 0.5 to5.0. Machine Direction (MD) and Transverse Direction (TD) tensilestrength are measured using Instron Model 4201 according to ASTM-882procedure.

In some embodiments, the porous film has a puncture strength of 400g/mil or greater. Puncture Strength is measured using Instron Model 4442based on ASTM D3763. The measurements are made across the width of themicroporous membrane (e.g., the porous substrate or film) and thepuncture strength defined as the force required to puncture the testsample

(2) Coating Layer

In one aspect, the coating layer may be an outermost coating layer ofthe separator, e.g., it may have no other different coating layersformed thereon, or the coating layer may have at least one otherdifferent coating layer formed thereon. For example, in someembodiments, a different polymeric coating layer may be coated over oron top of the coating layer formed on at least one surface of the poroussubstrate. In some embodiments, that different polymeric coating layermay comprise, consist of, or consist essentially of at least one ofpolyvinylidene difluoride (PVdF) or polycarbonate (PC).

In some embodiments, the coating layer is applied over top of one ormore other coating layers that have already been applied to at least oneside of the porous substrate. For example, in some embodiments, theselayers that have already been applied to a the porous substrate arethin, very thin, or ultra-thin layers of at least one of an inorganicmaterial, an organic material, a conductive material, a semi-conductivematerial, a non-conductive material, a reactive material, or mixturesthereof. In some embodiments, these layer(s) are metal or metaloxide-containing layers. In some preferred embodiments, ametal-containing layer and a metal-oxide containing layer, e.g., a metaloxide of the metal used in the metal-containing layer, are formed on theporous substrate before a coating layer comprising a coating compositiondescribed herein is formed. Sometimes, the total thickness of thesealready applied layer or layers is less than 5 microns, sometimes, lessthan 4 microns, sometimes less than 3 microns, sometimes less than 2microns, sometimes less than 1 micron, sometimes less than 0.5 microns,sometimes less than 0.1 microns, and sometimes less, than 0.05 microns.

In some embodiments, the thickness of the coating layer formed from thecoating compositions described hereinabove, is less than about 12 μm,sometimes less than 10 μm, sometimes less than 9 μm, sometimes less than8 μm, sometimes less than 7 μm, and sometimes less than 5 μm. In atleast certain selected embodiments, the coating layer is less than 4 μm,less than 2 μm, or less than 1 μm.

The coating method is not so limited, and the coating layer describedherein may be coated onto a porous substrate, e.g., as described herein,by at least one of the following coating methods: extrusion coating,roll coating, gravure coating, printing, knife coating, air-knifecoating, spray coating, dip coating, or curtain coating. The coatingprocess may be conducted at room temperature or at elevatedtemperatures.

The coating layer may be any one of nonporous, nanoporous, microporous,mesoporous or macroporous. The coating layer may have a JIS Gurley of10,000 or less, 1,000 or less, 700 or less, sometimes 600 or less, 500or less, 400 or less, 300 or less, 200 or less, or 100 or less. For anonporous coating layer, the JIS Gurley can be 800 or more, 1,000 ormore, 5,000 or more, or 10,000 or more (i.e., “infinite Gurley”) For anonporous coating layer, although the coating is nonporous when dry, itis a good ionic conductor, particularly when it becomes wet withelectrolyte.

In some embodiments, the coating layer may be a monolayer that is onemolecule thick, where the molecule is at least one of (i) a matrixmaterial or a polymeric binder, (ii) heat-resistant particles, or (iii)at least one component selected from the group consisting of across-linker, a low-temperature shutdown agent, an adhesion agent, and athickener.

In some embodiments, the coating is a continuous coating covering 10% ormore, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more,70% or more, 80% or more, 90% or more, or 100% of the porous membranesurface on at least one side.

In some embodiments, the coating is a discontinuous coating covering 1%or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more,50% or more, 60% or more, 70% or more, 80% or more, or 90% or more ofthe porous membrane surface on at least one side.

The coating, in some preferred embodiments, blocks or prevents dendritegrowth or shorts caused by dendrites. In some embodiments, this may meanthat the coating is tortuous or has no pin holes. In other words, thecoating does not have any pores where the tortuosity is 1. Tortuosityis, in some embodiments, greater than 1, greater than 1.1, greater than1.2, greater than 1.3, greater than 1.4, greater than 1.5, greater than1.6, greater than 1.7, greater than 1.8, greater than 1.9, or greaterthan 2.0.

Composite, Vehicle, or Device

A composite, jelly roll, pancake, or system comprising any separator asdescribed hereinabove and one or more electrodes, e.g., an anode, acathode, or an anode and a cathode, provided in direct contacttherewith. The type of electrodes are not so limited. For example theelectrodes can be those suitable for use in a lithium ion secondarybattery.

A lithium-ion battery according to some embodiments herein is shown inFIG. 7.

A section view of cylindrical lithium battery according to someembodiments herein is shown in FIG. 14.

In FIG. 14, a lithium ion or lithium metal cylindrical cell 10comprises, for example, a lithium metal or alloy anode 12, a cathode 14,and a separator 16 disposed between anode 12 and cathode 14, all ofwhich is packaged within a can 20. The illustrated cell 10 is acylindrical cell or ‘jelly roll’ cell, but the invention is not solimited. Other configurations, for example, prismatic cells, buttoncells, pouch cells, stacked cells, or polymer cells are also included.The cell may be a primary (single use) or secondary (rechargeable) cellor battery. Additionally, not shown is the electrolyte. The electrolytemay be a liquid (organic or inorganic), or a gel (or polymer). Theinvention will be, for convenience, described with regard to acylindrical cell with a liquid organic electrolyte, but it is not solimited and may find use in other cell types (e.g. energy storagesystem, combined cell and capacitor) and configurations.

A suitable anode 12 may be any anode and can in at least one embodimenthave an energy capacity greater than or equal to preferably 372 mAh/g,preferably ≥700 mAh/g, and most preferably ≥1000 mAH/g. The anode may beconstructed from a lithium metal foil or a lithium alloy foil (e.g.lithium aluminum alloys), or a mixture of a lithium metal and/or lithiumalloy and materials such as carbon (e.g. coke, graphite), nickel,copper. The anode is in at least one embodiment preferably not madesolely from intercalation compounds containing lithium or insertioncompounds containing lithium.

A suitable cathode 14 may be any cathode compatible with the anode andin at least one embodiment may include an intercalation compound, aninsertion compound, or an electrochemically active polymer. Suitableintercalation materials include, for example, MoS₂, FeS₂, MnO₂, TiS₂,NbSe₃, LiCoO₂, LiNiO₂, LiMn₂O₄, V₆O₁₃, V₂O₅, and CuCl₂. Suitablepolymers include, for example, polyacetylene, polypyrrole, polyaniline,and polythiopene.

The electrolyte may be liquid (organic or inorganic), or gel (orpolymer). Typically, the electrolyte preferably primarily consists of asalt and a medium (e.g. in a liquid electrolyte, the medium may bereferred to as a solvent; in a gel electrolyte, the medium may be apolymer matrix). The salt may be a lithium salt. The lithium salt mayinclude, for example, LiPF₆, LiAsF₆, LiCF₃SO₃, LiN(CF₃SO₃)₃, LiBF₆, andLiClO₄, BETTE electrolyte (commercially available from 3M Corp. ofMinneapolis, Minn.) and combinations thereof. Solvents may include, forexample, ethylene carbonate (EC), propylene carbonate (PC), EC/PC,2-MeTHF(2-methyltetrahydrofuran)/EC/PC, EC/DMC (dimethyl carbonate),EC/DME (dimethyl ethane), EC/DEC (diethyl carbonate), EC/EMC(ethylmethyl carbonate), EC/EMC/DMC/DEC, EC/EMC/DMC/DEC/PE, PC/DME, andDME/PC. Polymer matrices may include, for example, PVDF (polyvinylidenefluoride), PVDF:THF (PVDF:tetrahydrofuran), PVDF:CTFE (PVDF:chlorotrifluoro ethylene), PVDF:HFP (PVDF:hexafluoropropylene), PAN(polyacrylonitrile), and PEO (polyethylene oxide).

Any separator, cell or battery described hereinabove may be incorporatedto any vehicle, e.g., an e-vehicle, or device, e.g., a cell phone orlaptop, that is completely or partially battery powered. Variousembodiments of the invention have been described in fulfillment of thevarious objects of the invention. It should be recognized that theseembodiments are merely illustrative of the principles of the presentinvention. Numerous modifications and adaptations will be readilyapparent to those skilled in the art without departing from the spiritand scope of this invention.

EXAMPLES (1) At Least the Following Coating Compositions are Envisioned

TABLE 1 CJ CM CS a b c d e f X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X XX X X CJ-heat-resistant particles, binder comprising a polymer derivedfrom a lactam, optionally with water, an aqueous solvent, or anon-aqueous solvent as a solvent. CM-heat-resistant particles and PVAbinder, optionally with water, an aqueous solvent, or a non-aqueoussolvent as a solvent. CS-heat-resistant particles with an acrylicbinder, optionally with water, an aqueous solvent, or a non-aqueoussolvent as a solvent a-any cross-linker described herein b-anylow-temperature shutdown agent described herein c-any adhesion agentdescribed herein d-any thickener described herein e-any frictionreducing agent described herein f-any high-temperature shutdown agentdescribed herein

(2) Exemplary Improved Shutdown Embodiments

As discussed hereinabove, adding a low-temperature shutdown agent and/ora high-temperature shutdown agent may extend the shutdown window of acoated separator, compared to its uncoated counterpart or a coatedcounterpart, wherein the coating does not comprise a low-temperatureshutdown agent and/or a high/temperature shutdown agent.

-   (a) In one exemplary embodiment, a coated battery separator    (Inventive Example) according to some embodiments described herein    was prepared. The coating composition comprises CJ and polyethylene    beads as a low-temperature shutdown agent (b), and was coated on a    trilayer porous substrate comprising a polypropylene (PP) layer, a    polyethylene (PE) layer, and a polypropylene (PP) layer. The    shutdown characteristics of this coated battery separator were    evaluated according to Electrical Resistance testing as described    herein and compared with those of the trilayer porous substrate    itself (i.e., an uncoated Comparative Example). The results are    shown in FIG. 8. FIG. 8 shows that the shutdown window of the    Comparative Example is from about 125° C. to about 175° C. When the    coating is applied, the lower endpoint of the shutdown window is    shifted from about 125° C. to about 95° C., i.e., a shift of about    30° C. The upper endpoint of the shutdown window for the Inventive    and Comparative Examples is about the same. Thus, overall, the    shutdown window of the Inventive Example is extended by almost 30°    C., resulting in a much safer battery separator.-   (b) In another exemplary embodiment, a coated separator (Inventive    Example) is prepared, whose coating comprises CJ and PVDF as a    high-temperature shutdown agent (f). The porous substrate for this    Example is the same as that described in example 2(a) hereinabove.    The shutdown window of this coated separator (Inventive Example) was    evaluated according to Electric Resistance testing as described    herein, and compared to the uncoated trilayer porous substrate or    separator (Comparative Example). The results are presented in    FIG. 9. In this embodiment, the shutdown window of the Inventive    Example is lowered by about 5° C. and the upper endpoint of the    shutdown window is extended to >180° C., e.g., a resistance of    greater than 10,000 Ω·cm² is obtained at temperatures>180° C., which    results in a very safe battery.-   (c) In another exemplary embodiment, two coated separators were    prepared by coating multilayer (trilayer) porous substrates    comprising PP-PE-PP and PE-PP-PE with a coating comprising CJ and    polyvinylpyrrolidone (PVP), e.g., a high-temperature shutdown agent,    on one side of the porous substrates. The coatings were 3 microns    thick. These are the Inventive Examples. The shutdown window of    these coated separators (Inventive Example shown in FIG. 10B) were    evaluated according to Electric Resistance testing as described    herein, and compared to the uncoated multilayer (trilayer) porous    substrates comprising PP-PE-PP and PE-PP-PE, respectively    (Comparative Examples shown in FIG. 10A and FIG. 10C). Extended    shutdown characteristics beyond 190° C. were observed for both the    one-side coated PP-PE-PP porous substrate and for the one-side    coated PE-PP-PE substrate.

(3) Exemplary Improved Shrinkage Embodiments

-   (a) The addition of at least thickeners and/or cross-linkers to the    coating compositions described herein reduces shrinkage of    separators comprising a coating layer made from these coating    compositions, including at high temperature. In Table 2 below, a    coating composition comprising CS only, CS and d (a thickener), and    CS, d, and a (a cross-linker) were prepared. In these compositions,    CS and the thickener are identical in these compositions. CS and the    thickner

Shrinkage is measured in the both the Machine direction (MD) andTransverse direction (TD) direction and is expressed as a % MD shrinkageand % TD shrinkage. For the “180° C. for 10 minutes” testing, the sampleis placed in an oven at 180° C. for 10 minutes and then tested asdescribed above for the “150° C. for 1 hour” testing. For the “180° C.for 20 minutes” testing, the sample is placed in an oven at 180° C. for20 minutes and then tested as described above for the “150° C. for 1hour” testing. Shrinkage may be measured for a one-side coated poroussubstrate or for a two-side coated porous substrate.

Thickness is measured in micrometers, using the Emveco Microgage 210-Amicrometer thickness tester and test procedure ASTM D374.

TABLE 2 CS CSd CSda One- Two- One- Two- One- Two- SAMPLE sided sidesided sided sided sided Thickness of 19.993 24.773 18.103 22.403 18.66324.57 Separator (um) 150° C. MD 29.53 1.39 6.73 0.81 2.73 0.68 1 h (%)TD 1.28 0.45 1.13 0.15 1.85 0.07 180° C. MD Not 4.91 50.55 1.76 46.301.35 10 min. measurable (%) TD Not 6.11 0.63 1.53 5.11 0.90 measurable180° C. MD Not 4.73 Not 0.38 50.10 0.77 20 min. measurable measurable(%) TD Not 3.61 Not 0.30 2.31 0.59 measurable measurable

(4) Exemplary Improved Coating Layer-to-Electrode Adhesion Embodiments

As discussed hereinabove, adding an adhesion agent to the coatingcompositions described herein increases adhesion of the coating layer toan electrode, e.g., an anode.

-   (a) An Inventive Example identical to that prepared in section 2(b)    hereinabove was prepared. Adhesion of the coating layer of this    Example to an anode was evaluated as described herein. The results    are shown in FIG. 11. FIG. 11 shows that a lot of electrode    material, i.e., from the anode, was transferred to the separator,    indicating good adhesion between the coating layer and the anode.

(5) Exemplary Improved Coating Layer-to-Porous Substrate AdhesiveStrength Embodiments

As discussed hereinabove, adding an adhesion agent to the coatingcompositions described herein increases adhesion of the coating layer tothe porous substrate, without pre-treating the porous substrate.

(6) Exemplary Improved Pin Removal Force Embodiments

As discussed hereinabove, for example, addition of a friction reducingagent to the coating compositions described herein may improve pinremoval force of coating layers (and separators comprising such coatinglayers).

Inventive Examples from section 2(c) hereinabove (Inventive Examples,i.e., one-side coated PP-PE-PP porous substrates and one-side coatedPE-PP-PE porous substrate) were compared to an uncoated PP-PE-PP poroussubstrate (Control). The pin removal test described herein was performedthree times to collect three data points, and the data is reported inTable 3 below.

TABLE 3 One-side Coated PP-PE- One-side Coated PE-PP- Control PP PorousSubstrate PE Porous Substrate Sample ID: Data: 1 3082 3427 1742 Data: 22660 3470 1758 Data: 3 2618 3437 1690 AVG(gf) 2787 3445 1730 STDEV 25723 36 MA(gf) 3082 3470 1758 MIN(gf) 2618 3427 1690 COUNT 3 3 3 % PRF 24%−38%

(7) Exemplary Improved Hot Tip Test Embodiments

As discussed hereinabove, the separators disclosed herein have improvedthermal stability as shown, for example, by desirable behavior in hottip hole propagation studies. The hot tip test measures the dimensionalstability of the separators under point heating condition. The testinvolves contacting the separators with a hot soldering iron tip andmeasuring the resulting hole. Smaller holes are more desirable.

-   -   (a) The hot tip test was performed on the embodiments from        section 2(c) hereinabove, and the results are reported in Table        4 below and FIG. 12. It was found that the one-side coated        PE-PP-PE and PP-PE-PP substrates (Inventive Examples) performed        better (smaller holes) than the uncoated control, which was an        uncoated PP-PE-PP porous substrate (Control).

TABLE 4 One-Sided Coated PE-PP-PE Porous One-Sided Coated PP- ControlSubstrate PE-PP Porous Substrate Run 1: 0.681 0.683 Run 2: 0.657 0.644Run 3: 0.565 0.688 Average(mm) 3.669 0.634 0.672

Selected aluminum oxide coatings on the separator can be fabricated by aphysical vapor deposition (PVD) process. Major advantages of PVD processover other conventional coating techniques include the following:

-   -   Roll to roll production; can be produced hundreds of        meters/minute;    -   Homogeneous, uniform coating with complete coverage;    -   Binder-free coating with less/no defects;    -   Thickness tunable from a few nanometers to micron thick.

Referring to FIG. 13, one example of an inventive separator 20 is shown.Separator 20 preferably comprises at least one ceramic composite layeror coating 22 and at least one polymeric microporous layer 24. Theceramic composite layer is preferably and may be, at least, adapted forpreventing shrinkage, oxidation, electronic shorting (e.g. direct orphysical contact of the anode and the cathode), and/or blocking dendritegrowth. The polymeric microporous layer may be and is preferably adaptedfor at least preventing direct or physical contact of the anode and thecathode under normal conditions, supporting desired battery performance,and/or blocking (or shutting down) ionic conductivity (or flow) betweenthe anode and the cathode at high temperature to prevent or stop thermalrunaway. Under typical battery or cell operating conditions, the ceramiccomposite layer 22 of separator 20 must be sufficiently ionicallyconductive to allow ionic flow between the anode and cathode, so thatcurrent, in desired quantities, may be generated by the cell. The layers22 and 24 should adhere well to one another, i.e. unintended separationshould not occur. The layers 22 and 24 may be formed by lamination,co-extrusion, deposition, such as PVD, CVD, or ALD, or coatingprocesses. Ceramic composite layer 22 may be a coating or a discretelayer, either having a thickness ranging from 0.001 micron to 50microns, preferably in the range of 0.01 micron to 25 microns, morepreferably in the range of 0.50 micron to 10 microns (and if theseparator is two side coated then possibly preferably in the range of0.25 micron to 5 microns on each side). Polymeric microporous layer 24is preferably a discrete membrane having a thickness ranging from 1micron to 50 microns, preferably in the range of 5 microns to 50microns, preferably in the range of 2 microns to 25 microns, preferablyin the range of 12 microns to 25 microns, and more preferably from 3microns to 12 microns. The overall thickness of separator 20 is in therange of 1 micron to 100 microns, preferably in the range of 5 micronsto 100 microns, preferably in the range of 2 microns to 50 microns,preferably in the range of 12 microns to 50 microns, and more preferablyin the range of 3 microns to 25 microns.

Ceramic composite layer 22 comprises a matrix material or binder 26having particles 28 such as inorganic or ceramic particle dispersedtherethrough. Ceramic composite layer 22 is porous or nonporous (itbeing understood that some matrix or binder materials swell and gell inelectrolyte and can transport ions even if the dry separator has a highGurley (even at 1,000 or at 10,000 Gurley) before being wet or wet outwith electrolyte), and ion conductivity of layer 22 is primarilydependent upon choice of the porosity, electrolyte, matrix material 26,and particles 28. The matrix material 26 or particles 28 of layer 22 mayeach be one component of a separator which, in part, prevents electronicshorting by preventing dendrite growth and by keeping the electrodesspaced apart at high temperature. The matrix material 26 may, inaddition, also serve as a gel electrolyte or polymer electrolyte (e.g.carry the electrolyte salt). The matrix material 26 preferably comprisesabout 0.5-95% by weight, preferably 5-80% by weight of the ceramiccomposite layer 22, and the inorganic particles 28 preferably comprisesabout 5-95.5% by weight, preferably 20-95% by weight of the layer 22.Preferably, composite layer 22 contains inorganic particles 10%-99% byweight, preferably 30%-75% by weight. Most preferably, composite layer22 contains inorganic particles 20%-98% by weight, preferably 40%-60% byweight.

The matrix material 26 may contain organic and/or inorganic particles,and in addition, may also include electrolyte particles or materialsand/or may serve as a gel electrolyte or polymer electrolyte (e.g. carrythe electrolyte salts) and/or as an adhesive (may adhere to theelectrode, may reduce gaps or spaces between the separator andelectrode, may provide even charge distribution, and/or may preventdendrite formation). The matrix material or binder 26 may preferablycomprise about 0.5-95% by weight, preferably 2-80% by weight of theceramic composite layer 22, and the particles 28 preferably formapproximately 5-95.5% by weight, preferably 20-98% by weight of thelayer 22. In one particular embodiment, the particles are coatedparticles with the binder material as the coating. In another particularembodiment, the particles are a mixture of two or more particle types orsizes.

The matrix material 26 may be ionically conductive or non-conductive,such as solvent or aqueous based polymers or binders such as PVDF,acrylics, polyamide, and/or any gel forming polymer suggested for use inlithium polymer batteries or in solid electrolyte batteries, copolymersthereof, and combinations, co-polymers, blends, or mixtures thereof. Thematrix material 26 may be selected from, for example, polyethylene oxide(PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE),polyurethane, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA),polytetraethylene glycol diacrylate, copolymers thereof, and mixturesthereof. The preferred matrix material is PVDF and/or PEO and theircopolymers. The PVDF copolymers include PVDF:HFP (polyvinylidenefluoride:hexafluoropropylene) and PVDF:CTFE (polyvinylidenefluoride:chlorotrifluoroethylene). Most preferred matrix materialsinclude PVDF:CTFE with less than 23% by weight CTFE, PVDF:HFP with lessthan 28% by weight HFP, any type of PEO, and combinations, blends,mixtures or co-polymers thereof. In one particular embodiment, thebinder may be a polyimide or polyamide, such as a solvent solublepolyimide or polyamide.

The inorganic particles 28 are normally considered nonconductive,however, these particles, when in contact with the electrolyte, maydevelop an ion conductive or superconductive surface which improves theion conductivity (reduces resistance) of the separator 20. The inorganicparticles 28 may be selected from, for example, silicon dioxide (SiO₂),aluminum oxide (Al₂O₃), boehmite, kaolin, clay, barium sulfate, calciumcarbonate (CaCO₃), titanium dioxide (TiO₂), SiS₂, SiPO₄, X-Raydetectable materials, kaolin clay, calcined clay, kaolinite, meta-stablealumina, or combinations, blends or mixtures thereof. The preferredinorganic particle may be boehmite, kaolin, SiO₂, Al₂O₃, barium sulfate,and/or CaCO₃. The particles may have an average particle size in therange of 0.001 micron to 25 microns, preferably in the range of 0.01micron to 2 microns, and most preferably in the range of 0.05 micron to0.5 microns.

The microporous polymeric layer 24 may be any of several types ofmicroporous membranes (e.g. single ply or multi-ply), sheets, films orlayers, for example, those Celgard® microporous polyolefin productsproduced by Celgard, LLC of Charlotte, N.C., or Hipore® microporouspolyolefin products produced by Asahi Kasei Corp. of Tokyo, Japan,and/or the like. The layer 24 may have a porosity in the range of10-90%, preferably in the range of 20-80%, more preferably in the rangeof 28-60%. The layer 24 may have an average pore size in the range of0.001 to 2 microns, preferably in the range of 0.02 to 2 micron,preferably in the range of 0.05 to 1 micron, more preferably in therange of 0.08 to 0.5 micron. The layer 24 may have a Gurley Number inthe range of preferably 5 to 150 sec, preferably 15 to 150 sec,preferably 10 to 80 sec, more preferably 30 to 60 sec. (Gurley Numberrefers to the time it takes for 10 cc of air at 12.2 inches of water topass through one square inch of membrane.) The layer 24 is preferablypolyolefinic. Preferred polyolefins include polyethylene andpolypropylene, or combinations, blends, co-polymers, block co-polymers,or mixtures thereof.

In accordance with at least certain selected embodiments, this inventionor application is directed to or provides new or improved coatings forporous substrates, including battery separators, capacitor separators,fuel cell membranes, textile materials, garment materials or layers,filtration materials, and the like, and new and/or improved coatedporous substrates, including battery separators, and more particularly,to new or improved coatings for porous substrates, including batteryseparators, capacitor separators, fuel cell membranes, textilematerials, garment materials or layers, filtration materials, and thelike which comprise at least (i) a polymeric binder, (ii) optionalorganic and/or inorganic compression resistant, dendrite resistant,and/or heat-resistant particles, and (iii) at least one componentselected from the group consisting of a cross-linker, a shutdown agent,a low-temperature shutdown agent, a high temperature shutdown agent, anadhesion agent, an X-Ray detectable element, a friction-reducing agent,and/or a thickener, and/or to new and/or improved coated poroussubstrates, including battery separators, where the coating comprises atleast (i) a polymeric binder, (ii) optional organic and/or inorganiccompression resistant, dendrite resistant, and/or heat-resistantparticles, and (iii) at least one component selected from the groupconsisting of a cross-linker, a shutdown agent, a low-temperatureshutdown agent, a high temperature shutdown agent, an adhesion agent, anX-Ray detectable element, a friction-reducing agent, and/or a thickener.

In accordance with at least certain objects, aspects or embodiments,there is described or shown certain new and/or improved coatings forporous substrates, including battery separators or separator membranes,and/or coated porous substrates, including coated battery separators,and/or batteries or cells including such coatings or coated separators,and/or related methods including methods of manufacture and/or of usethereof are disclosed. Also, new or improved coatings for poroussubstrates, including battery separators, which comprise at least amatrix material or a polymeric binder, and heat-resistant particles withadditional additives, materials or components, and/or to new or improvedcoated porous substrates, including battery separators, where thecoating comprises at least a matrix material or a polymeric binder, andheat-resistant particles with additional additives, materials orcomponents are disclosed. Further, new or improved coatings for poroussubstrates, including battery separators, and new and/or improved coatedporous substrates, including battery separators, new or improvedcoatings for porous substrates, including battery separators, whichcomprise at least (i) a matrix material or a polymeric binder, (ii)heat-resistant particles, and (iii) at least one component selected fromthe group consisting of a cross-linker, a low-temperature shutdownagent, an adhesion agent, and a thickener, and new and/or improvedcoated porous substrates, including battery separators, where thecoating comprises at least (i) a matrix material or a polymeric binder,(ii) heat-resistant particles, and (iii) at least one component selectedfrom the group consisting of a cross-linker, a low-temperature shutdownagent, an adhesion agent, a thickener, a friction-reducing agent, ahigh-temperature shutdown agent are disclosed. Polymer matrices orbinders may include, for example, PVDF (polyvinylidene fluoride),PVDF:THF (PVDF:tetrahydrofuran), PVDF:CTFE (PVDF: chlorotrifluoroethylene), PVDF:HFP (PVDF:hexafluoropropylene), PAN (polyacrylonitrile),PVA (polyvinyl alcohol), PTFE (polytetrafluoroethylene), PFA(perfluoroalkoxy), fluoropolymer, acrylic, PO (polyolefin), PE(polyethylene), PP (polypropylene), PMP (polymethylpentene), PEO(polyethylene oxide), polyacrylic acid (PAA), polymethylmethacrylate(PMMA), polyacrylonitrile (PAN), polymethyl acrylate (PMA), andcomposites, combinations, mixtures, blends, copolymers, or blockcopolymers thereof.

In other preferred embodiments, the polymeric binder may comprise,consist of, or consist essentially of carboxymethyl cellulose (CMC), anisobutylene polymer, latex,

In accordance with at least certain objects, aspects or embodiments,there is described or shown certain new and/or improved methods. Forexample, a method for detecting the position of a separator relative toelectrodes in a secondary lithium battery comprising the steps of:providing a secondary lithium battery including a positive electrode, anegative electrode, a X-ray sensitive separator located between theelectrodes, and a can or pouch housing the electrodes and separator, theX-ray sensitive separator comprising a microporous membrane having aX-ray detectable element dispersed therein or thereon, the X-raydetectable element comprising at least 1 and no greater than 80 weightpercent of the membrane; subjecting the secondary lithium battery toX-ray radiation; determining the position of the separator relative tothe electrodes; and approving or rejecting the secondary lithium batterybased upon the position of the separator relative to the electrodes.

The method above wherein the X-ray detectable element comprising 2 to 70weight % of the membrane.

The method above wherein the X-ray detectable element comprising 5 to 50weight % of the membrane.

The method above wherein the X-ray detectable element included in acoating on the membrane.

The method above wherein the X-ray detectable element being selectedfrom the group consisting of metal, metal oxide, metal phosphate, metalcarbonate, X-ray fluorescent material, metal salt, metal sulfate, ormixtures thereof, and any of the foregoing metals being selected fromthe group consisting of Zn, Ti, Mn, Ba, Ni, W, Hg, Si, Cs, Sr, Ca, Rb,Ta, Zr, Al, Pb, Sn, Sb, Cu, Fe, and mixtures thereof.

The method above wherein the X-ray detectable element preferably beingbarium sulfate.

The method above wherein the X-ray detectable element is in a coating onat least one side of the membrane.

The method above wherein the coating is a ceramic coating.

The method above wherein the X-ray detectable element is at least one ofdispersed therein, coated thereon, or added thereto.

A new and/or improved separator as described herein may have or exhibitone or more of the following characteristics or improvements: (1)desirable level of porosity as observed by SEMs and as measured; (2)desirable Gurley numbers to show permeability; (3) desirable thickness;(4) a desired level of coalescing of the polymeric binder such that thecoating is improved relative to known coatings; (4) desirable propertiesdue to processing of the coated separator, including, but not limitedto, how the coating is mixed, how the coating is applied to thesubstrate, how the coating is dried on the substrate, if another coatingor material is applied over the coating (for example, a sticky (at leastwhen wet with electrolyte) or adhesive coating, stripes or spots areadded), and/or if the coating is (coatings, or layers are) compressed orcalendered; (5) improved thermal stability as shown, for example, bydesirable behavior in hot tip hole propagation studies; (6) reducedshrinkage when used in a lithium battery, such as a lithium ion battery;(7) improved adhesion between the heat-resistant particles in thecoating; (8) improved adhesion between the coating and the substrate;(9) improved adhesion between the coated separator and one or bothelectrodes of a battery; (10) improved pin removal force and/orcoefficient of friction (for example, reduced pin removal force and/orreduced coefficient of friction as compared to uncoated substrate or totypical coated materials); (11) improved wettability or wicking ofelectrolyte; and/or (12) improved oxidation resistance and/or highvoltage performance. The separator may be coated on one side (OSC), ontwo sides (TSC), have a ceramic coating (CCS) on one side (OSC CCS),have a ceramic coating (CCS) on both sides (TSC CCS), have a ceramiccoating (CCS) on one side (OSC CCS) and have a polymer or sticky coating(PCS) on the other side (OSC CCS/OSC PCS), have a ceramic coating (CCS)on both sides (TSC CCS) and have a polymer or sticky coating (PCS) ontop of one side CCS (TSC CCS/OSC PCS), have a ceramic coating (CCS) onboth sides (TSC CCS) and have a polymer or sticky coating (PCS) on topof each of the CCS (TSC CCS/TSC PCS), have CCS on top of a physicalvapor deposition (PVD), chemical vapor deposition (CVD) or atomic layerdeposition (ALD) on at least one side (OSC VAD/OSC CCS), have CCS on topof a physical vapor deposition (PVD), chemical vapor deposition (CVD) oratomic layer deposition (ALD) on both sides (TSC VAD/TSC CCS), have PCSon top of a physical vapor deposition (PVD), chemical vapor deposition(CVD) or atomic layer deposition (ALD) on at least one side at least oneside (OSC VAD/OSC PCS), have PCS on top of a physical vapor deposition(PVD), chemical vapor deposition (CVD) or atomic layer deposition (ALD)on both sides (TSC VAD/TSC PCS), have PCS on top of a physical vapordeposition (PVD), chemical vapor deposition (CVD) or atomic layerdeposition (ALD) on one side and have CCS on top of a physical vapordeposition (PVD), chemical vapor deposition (CVD) or atomic layerdeposition (ALD) on the other side (TSC VAD/OSC PCS/OSC CCS), have PCSon top of the CCS, have CCS on top of the PCS, have the VAD on top ofthe CCS, have the VAD on top of the PCS, and/or the like. The VAD can beorganic and/or inorganic. The CCS particles can be organic and/orinorganic. For example, an X-Ray detectable particle or agent can bemixed with PE particles or beads. It may be preferred in one embodimentto have CCS on one side and PCS on the other side, in a secondembodiment to have CCS on both sides, in a third embodiment to have PCSon both sides, in a fourth embodiment to have CCS with PCS on top on oneside and just PCS on the other side, in a fifth embodiment to have CCSwith PCS on top on both sides, to have a sticky CCS on both sides (theCCS includes at least one sticky component or binder which may be thesame or different on each side [the anode may prefer one sticky materialwhile the cathode prefers a different sticky material]), the separatorsmay be pieces, leafs, sleeves, pockets, envelopes, S wrap, Z fold,sheets, rolls, flexible, rigid, and/or the like, and/or all theseparators in a battery may be of the same construction or of differentconstructions. One battery maker may put the CCS against the anode andthe PCS or VAD against the cathode, while another battery maker may putthe CCS against the cathode. It is contemplated that depending on thecell type and/or on the battery energy and/or voltage, that the CCS, PCSor VAD may be placed against the anode and/or the CCS, PCS or VAD may beplaced against the cathode. These objects, aspects or embodiments,and/or other related attributes of an improved coated separator aredescribed in more detail in other parts of this application.

In accordance with various aspects, objects or embodiments, there aredescribed or provided new and/or improved coatings, layers or treatmentsfor porous substrates, including battery separators or separatormembranes, and/or coated or treated porous substrates, including coatedbattery separators, and/or batteries or cells including such coatings orcoated separators, and/or related methods including methods ofmanufacture and/or of use thereof are disclosed. Also, new or improvedcoatings for porous substrates, including battery separators, whichcomprise at least a matrix material or a polymeric binder, andheat-resistant particles with additional additives, materials orcomponents, and/or to new or improved coated or treated poroussubstrates, including battery separators, where the coating comprises atleast a matrix material or a polymeric binder, and heat-resistantparticles with additional additives, materials or components aredisclosed. Further, new or improved coatings for porous substrates,including battery separators, and new and/or improved coated poroussubstrates, including battery separators, new or improved coatings forporous substrates, including battery separators, which comprise at least(i) a matrix material or a polymeric binder, (ii) heat-resistantparticles, and (iii) at least one component selected from the groupconsisting of a cross-linker, a low-temperature shutdown agent, anadhesion agent, and a thickener, and new and/or improved coated poroussubstrates, including battery separators, where the coating comprises atleast (i) a matrix material or a polymeric binder, (ii) heat-resistantparticles, and (iii) at least one component selected from the groupconsisting of a cross-linker, a low-temperature shutdown agent, anadhesion agent, a thickener, a friction-reducing agent, and ahigh-temperature shutdown agent are disclosed.

Various embodiments of the present invention have been described infulfillment of the various objectives of the invention. It should berecognized that these embodiments are merely illustrative of theprinciples of the present invention. Numerous modifications andadaptations thereof will be readily apparent to those skilled in the artwithout departing from the spirit and scope of the invention.

1.-956. (canceled)
 957. A separator for a high energy rechargeablelithium battery comprises: at least one ceramic composite layer, saidlayer being formed from a coating composition which includes a matrixmaterial or a polymeric binder, heat-resistant particles, and across-linker, said layer being adapted to at least block dendrite growthand to prevent electronic shorting; and at least one polyolefinicmicroporous layer, said layer being adapted to block ionic flow betweenan anode and a cathode.
 958. The separator according to claim 957wherein said coating composition comprises between 20% to 95% by weightof said heat-resistant particles and between 5% to 80% by weight of saidmatrix material or polymeric binder.
 959. The separator according toclaim 957 wherein said heat-resistant particles are selected from thegroup consisting of SiO₂, Al₂O₃, CaCO₃, TiO₂, SiS₂, SiPO₄, and mixturesthereof.
 960. The separator according to claim 957 wherein said matrixmaterial is selected from the group consisting of polyethylene oxide,polyvinylidene fluoride, polytetrafluoroethylene, polyurethane,polyacrylonitrile, polymethylmethacrulate, polytetraethylene glycoldiacrylate, copolymers thereof, and mixtures thereof.
 961. The separatoraccording to claim 957 wherein said polyolefinic microporous layer is apolyolefinic membrane or a polyethylene membrane.
 962. The separatoraccording to claim 957 wherein said polymeric binder comprises water asthe solvent, an aqueous solvent, or a nonaqueous solvent.
 963. Theseparator according to claim 957 wherein the polymeric binder comprisesat least one selected from the group consisting of a polylactam polymer,polyvinyl alcohol (PVA), Polyacrylic acid (PAA), Polyvinyl acetate(PVAc), carboxymethyl cellulose (CMC), an isobutylene polymer, anacrylic resin, and latex; or or wherein the polymeric binder comprises apolylactam polymer, which is a homopolymer, co-polymer, block polymer,or block co-polymer derived from a lactam, wherein the homopolymer orcopolymer derived from a lactam may be at least one selected from thegroup consisting of polyvinylpyrrolidone (PVP), polyvinylcaprolactam(PVCap), and polyvinyl-valerolactam.
 964. The separator according toclaim 963 wherein the polymeric binder comprises a polylactam of Formula(1): wherein R¹, R², R³, and R⁴ can be alkyl or aromatic substituentsand R⁵ can be alkyl, aryl, or fused ring; and

wherein the preferred polylactam can be a homopolymer or a co-polymerwhere co-polymeric group X can be a derived from vinyl, a substituted orun-substituted alkyl vinyl, vinyl alcohol, vinyl acetate, acrylic acid,alkyl acrylate, acrylonitrile, maleic anhydride, maleic imide, styrene,polyvinylpyrrolidone (PVP), polyvinylvalerolactam, polyvinylcaprolactam(PVCap), polyamide, or polyimide; wherein m can be an integer between 1and 10, preferably between 2 and 4, and wherein the ratio of I to n issuch that 0≤I:n≤10 or 0≤I:n≤1; or wherein the polymeric coatingcomprises a polylactam according to Formula (2) and a catalyst:

wherein R¹, R², R³, and R⁴ can be alkyl or aromatic substituents; R⁵ canbe alkyl, aryl, or fused ring; m can be an integer between 1 and 10,preferably between 2 and 4, and wherein the ratio of I to n is such that0≤I:n≤10 or 0≤I:n≤1, and X is an epoxide or an alkyl amine wherein insome embodiments, X may be an epoxide and the catalyst may comprise analkyl amine or epoxide.
 965. The separator according to claim 957wherein the polymeric binder comprises polyvinyl alcohol (PVA),polyacrylic acid (PAA), polyvinyl acetate (PVAc), carboxymethylcellulose (CMC), an isobutylene polymer, acrylic resin, and/or latex.966. The separator according to claim 957 wherein the heat-resistantparticles comprise an organic material or a mixture of an organicmaterial and an inorganic material, and the organic material is at leastone selected from the group consisting of: a polyimide resin, a melamineresin, a phenol resin, a polymethyl methacrylate (PMMA) resin, apolystyrene resin, a polydivinylbenzene (PDVB) resin, carbon black, andgraphite.
 967. The separator according to claim 957 wherein the ratio ofheat-resistant particles to binder in the coating composition is 50:50to 99:1 or wherein 0.01 to 99.99% of the surface area of at least one ofthe heat-resistant particles is coated by the binder.
 968. The separatoraccording to claim 957 wherein the cross-linker comprising multiplereactive groups, and wherein the cross-linker may be an epoxycross-linker comprising multiple reactive epoxy groups or thecross-linker may be an acrylate cross-linker comprises multiple reactiveacrylate groups.
 969. The separator according to claim 957 wherein theceramic composite layer further comprises another different coatinglayer formed thereon.
 970. A secondary lithium ion battery comprisingthe separator of claim
 957. 971. A composite comprising the separator ofclaim 957 direct contact with an electrode for a secondary lithium ionbattery.
 972. A vehicle or device comprising the separator of claim 957.973. A high energy rechargeable lithium battery comprising: an anodecontaining lithium metal or lithium-alloy or a mixtures of lithium metaland/or lithium alloy and another material; a cathode; a separatoraccording to claim 957 disposed between said anode and said cathode; andan electrolyte in ionic communication with said anode and said cathodevia said separator.
 974. A separator for an energy storage system,wherein the separator comprises at least one ceramic composite layer orcoating, said layer including a coating composition of 20-95% by weightof heat-resistant particles selected from the group consisting of SiO₂,Al₂O₃, CaCO₃, TiO₂, SiS₂, SiPO₄ and the like, and mixtures thereof,5-80% by weight of a matrix material or a polymeric binder, and across-linker; said matrix material selected from the group consisting ofpolyethylene oxide, polyvinylidene fluoride, polytetrafluoroethylene,copolymers of the foregoing, and mixtures thereof, said layer beingadapted to at least block dendrite growth and to prevent electronicshorting; and at least one polyolefinic microporous layer having aporosity in the range of 20-80%, an average pore size in the range of0.02 to 2 microns, and a Gurley Number in the range of 15 to 150 sec,said layer being adapted to block ionic flow between an anode and acathode; or the separator comprises at least one ceramic composite layerwherein the ceramic composite layer is a coating with a thickness in therange of about 0.01 to 25 microns and comprises: a coating compositionof heat-resistant particles having an average particle size in the rangeof 0.001 to 24 microns and a cross-linker in a matrix material or apolymeric binder, wherein the heat-resistant particles comprise silicondioxide (SiO₂), aluminum oxide (Al₂O₃), calcium carbonate (CaCO₃),titanium dioxide (TiO₂), SiS₂, SiPO₄, or mixtures thereof, and whereinthe ceramic composite layer is adapted to at least block dendrite growthafter repetitive charge-discharge cycling and to prevent electronicshorting throughout repetitive charge-discharge cycling throughout thecycle life of the rechargeable battery; and at least one polyolefinicmicroporous layer wherein the polyolefinic microporous layer comprises apolyolefinic membrane of at least one of polyethylene or polypropyleneand is adapted to shut down and block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer wherein the ceramic composite layer includes a coating compositionof heat-resistant particles and a cross-linker in a matrix material or apolymeric binder and wherein the ceramic composite layer is adapted toat least block dendrite growth after repetitive charge-discharge cyclingand to prevent electronic shorting; and at least one polyolefinicmicroporous layer wherein the layer is adapted to block ionic flowbetween an anode and a cathode; or the separator comprises at least oneceramic composite layer, wherein the ceramic composite layer comprises:a coating composition of about 20-95% by weight of heat-resistantparticles, about 5-80% by weight of a matrix material or a polymericbinder, and a cross-linker, wherein the ceramic composite layer isadapted to at least block dendrite growth after repetitivecharge-discharge cycling and thereby to prevent electronic shorting; andat least one polyolefinic microporous layer having a porosity in therange of about 20-80%, an average pore size in the range of about 0.02to 2 microns, and wherein the polyolefinic microporous layer is adaptedto block ionic flow between an anode and a cathode; or the separatorcomprises at least one ceramic composite layer wherein the ceramiccomposite layer is a coating with a thickness in the range of about 0.01to 25 microns and comprises: a coating composition of heat-resistantparticles having an average particle size in the range of 0.001 to 24microns and a cross-linker in a matrix material or a polymeric binder;said matrix material comprises polyethylene oxide (PEO), polyvinylidenefluoride (PVDF), polytetrafluoroethylene (PTFE), polyurethane,polyacrylonitrile (PAN), polymethylmethacrylate (PMMA),polytetraethylene glycol diacrylate, copolymers thereof, or mixturesthereof, wherein the heat-resistant particles comprise silicon dioxide(SiO₂), aluminum oxide (Al₂O₃), calcium carbonate (CaCO₃), titaniumdioxide (TiO₂), SiS₂, SiPO₄, or mixtures thereof, and wherein theceramic composite layer is adapted to at least block dendrite growthafter repetitive charge-discharge cycling and thereby to preventelectronic shorting by preventing direct contact between an anode and acathode throughout repetitive charge-discharge cycling throughout thecycle life of the battery; and at least one polyolefinic microporouslayer wherein the polyolefinic microporous layer comprises a shutdownpolyolefinic membrane of polyethylene or polypropylene and is adapted toblock ionic flow between the anode and the cathode; or the separatorcomprises at least one ceramic composite layer wherein the ceramiccomposite layer is a coating with a thickness in the range of about 0.01to 25 microns and comprises: a coating composition of heat-resistantparticles having an average particle size in the range of 0.001 to 24microns and a cross-linker in a matrix material or a polymeric binder,wherein the matrix material comprises PVDF (polyvinylidene fluoride),PAN (polyacrylonitrile), PEO (polyethylene oxide), or copolymers ormixtures thereof, and wherein the ceramic composite layer is adapted toat least block dendrite growth after repetitive charge-discharge cyclingand to prevent electronic shorting throughout repetitivecharge-discharge cycling throughout the cycle life of the rechargeablebattery; and at least one polyolefinic microporous layer wherein thepolyolefinic microporous layer comprises a polyolefinic membrane of atleast one of polyethylene or polypropylene and is adapted to shut downand block ionic flow between the anode and the cathode; or the separatorcomprises at least one ceramic composite layer, said layer being formedfrom a coating composition which includes a matrix material or apolymeric binder; heat-resistant particles; and an adhesion agent; saidlayer being adapted to at least block dendrite growth and to preventelectronic shorting; and at least one polyolefinic microporous layer,said layer being adapted to block ionic flow between an anode and acathode; or the separator comprises at least one ceramic composite layerwherein the ceramic composite layer is a coating with a thickness in therange of about 0.01 to 25 microns and comprises: a mixture ofheat-resistant particles having an average particle size in the range of0.001 to 24 microns and an adhesion agent in a polymer matrix materialor a polymeric binder, wherein the heat-resistant particles comprisesilicon dioxide (SiO₂), aluminum oxide (Al₂O₃), calcium carbonate(CaCO₃), titanium dioxide (TiO₂), SiS₂, SiPO₄, or mixtures thereof, andwherein the ceramic composite layer is adapted to at least blockdendritegrowth after repetitive charge-discharge cycling and to preventelectronic shorting throughout repetitive charge-dischargecyclingthroughout the cycle life of the rechargeable battery; and at least onepolyolefinic microporous layer wherein the polyolefinic microporouslayer comprises a polyolefinic membrane of at least one of polyethyleneor polypropylene and is adapted to shut down and block ionic flowbetween the anode and the cathode; or the separator comprises at leastone ceramic composite layer wherein the ceramic composite layer includesa mixture of heat-resistant particles and an adhesion agent in a matrixmaterial or a polymeric binder, and wherein the ceramic composite layeris adapted to at least block dendrite growth after repetitivecharge-discharge cycling and to prevent electronic shorting; and atleast one polyolefinic microporous layer wherein the layer is adapted toblock ionic flow between an anode and a cathode; or the separatorcomprise at least one ceramic composite layer, wherein the ceramiccomposite layer comprises: a mixture of about 20-95% by weight ofheat-resistant particles, about 5-80% by weight of a matrix material ora polymeric binder; and an adhesion agent, wherein the ceramic compositelayer is adapted to at least block dendrite growth after repetitivecharge-discharge cycling and thereby to prevent electronic shorting; andat least one polyolefinic microporous layer having a porosity in therange of about 20-80%, an average pore size in the range of about 0.02to 2 microns, and wherein the polyolefinic microporous layer is adaptedto block ionic flowbetween an anode and a cathode; or the separatorcomprises at least one ceramic composite layer wherein the ceramiccomposite layer is a coating with a thickness in the range of about 0.01to 25 microns and comprises: a mixture of heat-resistant particleshaving an average particle size in the range of 0.001 to 24 microns andan adhesion agent in a matrix material or a polymeric binder, the saidmatrix material comprises polyethylene oxide (PEO), polyvinylidenefluoride (PVDF), polytetrafluoroethylene (PTFE), polyurethane,polyacrylonitrile (PAN), polymethylmethacrylate (PMMA),polytetraethylene glycol diacrylate, copolymers thereof, or mixturesthereof, wherein the heat-resistant particles comprise silicon dioxide(SiO₂), aluminum oxide (Al₂O₃), calcium carbonate (CaCO₃), titaniumdioxide (TiO₂), SiS₂, SiPO₄, and wherein the ceramic composite layer isadapted to at least block dendrite growth after repetitivecharge-discharge cycling and thereby to prevent electronic shorting bypreventing direct contact between an anode and a cathode throughoutrepetitive charge-discharge cycling throughout the cycle life of thebattery; and at least one polyolefinic microporous layer wherein thepolyolefinic microporous layer comprises a shutdown polyolefinicmembrane of polyethylene or polypropylene and is adapted to block ionicflow between the anode and the cathode; or the separator comprises atleast one ceramic composite layer wherein the ceramic composite layer isa coating with a thickness in the range of about 0.01 to 25 microns andcomprises: a mixture of heat-resistant particles having an averageparticle size in the range of 0.001 to 24 microns and an adhesion agentin a polymer matrix material or a polymeric binder, wherein the polymermatrix material comprises PVDF (polyvinylidene fluoride), PAN(polyacrylonitrile), PEO (polyethylene oxide), or copolymers or mixturesthereof, and wherein the ceramic composite layer is adapted to at leastblockdendrite growth after repetitive charge-discharge cycling and toprevent electronic shorting throughout repetitivecharge-dischargecycling throughout the cycle life of the rechargeablebattery; and at least one polyolefinic microporous layer wherein thepolyolefinic microporous layer comprises a polyolefinic membrane of atleast one of polyethylene or polypropylene and is adapted to shut downand block ionic flow between the anode and the cathode; or the separatorcomprise at least one ceramic composite layer, said layer being formedfrom a coating composition which includes a matrix material or apolymeric binder; heat-resistant particles; and a friction reducingagent; said layer being adapted to at least block dendrite growth and toprevent electronic shorting; and at least one polyolefinic microporouslayer, said layer being adapted to block ionic flow between an anode anda cathode; or the separator comprises at least one ceramic compositelayer wherein the ceramic composite layer is a coating with a thicknessin the range of about 0.01 to 25 microns and comprises: a mixture ofheat-resistant particles having an average particle size in the range of0.001 to 24 microns and a friction reducing agent in a polymer matrixmaterial or a polymeric binder, wherein the heat-resistant particlescomprise silicon dioxide (SiO₂), aluminum oxide (Al₂O₃), calciumcarbonate (CaCO₃), titanium dioxide (TiO₂), SiS₂, SiPO₄, or mixturesthereof, and wherein the ceramic composite layer is adapted to at leastblockdendrite growth after repetitive charge-discharge cycling and toprevent electronic shorting throughout repetitivecharge-dischargecycling throughout the cycle life of the rechargeablebattery; and at least one polyolefinic microporous layer wherein thepolyolefinic microporous layer comprises a polyolefinic membrane of atleast one of polyethylene or polypropylene and is adapted to shut downand block ionic flow between the anode and the cathode; or the separatorcomprises at least one ceramic composite layer wherein the ceramiccomposite layer includes a mixture of heat-resistant particles and afriction reducing agent in a matrix material or a polymeric binder, andwherein the ceramic composite layer is adapted to at least blockdendrite growth after repetitive charge-discharge cycling and to preventelectronic shorting; and at least one polyolefinic microporous layerwherein the layer is adapted to block ionic flow between an anode and acathode; or the separator comprises at least one ceramic compositelayer, wherein the ceramic composite layer comprises: a mixture of about20-95% by weight of heat-resistant particles, about 5-80% by weight of amatrix material or a polymeric binder; and a friction reducing agent,wherein the ceramic composite layer is adapted to at least blockdendrite growth after repetitive charge-discharge cycling and thereby toprevent electronic shorting; and at least one polyolefinic microporouslayer having a porosity in the range of about 20-80%, an average poresize in the range of about 0.02 to 2 microns, and wherein thepolyolefinic microporous layer is adapted to block ionic flow between ananode and a cathode; or the separator comprises at least one ceramiccomposite layer wherein the ceramic composite layer is a coating with athickness in the range of about 0.01 to 25 microns and comprises: amixture of heat-resistant particles having an average particle size inthe range of 0.001 to 24 microns and a friction reducing agent in amatrix material or a polymeric binder, the said matrix materialcomprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF),polytetrafluoroethylene (PTFE), polyurethane, polyacrylonitrile (PAN),polymethylmethacrylate (PMMA), polytetraethylene glycol diacrylate,copolymers thereof, or mixtures thereof, wherein the heat-resistantparticles comprise silicon dioxide (SiO₂), aluminum oxide (Al₂O₃),calcium carbonate (CaCO₃), titanium dioxide (TiO₂), SiS₂, SiPO₄, andwherein the ceramic composite layer is adapted to at least blockdendrite growth after repetitive charge-discharge cycling and thereby toprevent electronic shorting by preventing direct contact between ananode and a cathode throughout repetitive charge-discharge cyclingthroughout the cycle life of the battery; and at least one polyolefinicmicroporous layer wherein the polyolefinic microporous layer comprises ashutdown polyolefinic membrane of polyethylene or polypropylene and isadapted to block ionic flow between the anode and the cathode; or theseparator comprises at least one ceramic composite layer wherein theceramic composite layer is a coating with a thickness in the range ofabout 0.01 to 25 microns and comprises: a mixture of heat-resistantparticles having an average particle size in the range of 0.001 to 24microns and a friction reducing agent in a polymer matrix material or apolymeric binder, wherein the polymer matrix material comprises PVDF(polyvinylidene fluoride), PAN (polyacrylonitrile), PEO (polyethyleneoxide), or copolymers or mixtures thereof, and wherein the ceramiccomposite layer is adapted to at least block dendrite growth afterrepetitive charge-discharge cycling and to prevent electronic shortingthroughout repetitive charge-dischargecycling throughout the cycle lifeof the rechargeable battery; and at least one polyolefinic microporouslayer wherein the polyolefinic microporous layer comprises apolyolefinic membrane of at least one of polyethylene or polypropyleneand is adapted to shut down and block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer, said layer being formed from a coating composition which includesa matrix material or a polymeric binder; heat-resistant particles; and ahigh-temperature shutdown agent; said layer being adapted to at leastblock dendrite growth and to prevent electronic shorting; and at leastone polyolefinic microporous layer, said layer being adapted to blockionic flow between an anode and a cathode; or the separator comprises atleast one ceramic composite layer wherein the ceramic composite layer isa coating with a thickness in the range of about 0.01 to 25 microns andcomprises: a mixture of heat-resisitant particles having an averageparticle size in the range of 0.001 to 24 microns and a high-temperatureshutdown agent in a polymer matrix material or a polymeric binder,wherein the heat-resisitant particles comprise silicon dioxide (SiO₂),aluminum oxide (Al₂O₃), calcium carbonate (CaCO₃), titanium dioxide(TiO₂), SiS₂, SiPO₄, or mixtures thereof, and wherein the ceramiccomposite layer is adapted to at least block dendrite growth afterrepetitive charge-discharge cycling and to prevent electronic shortingthroughout repetitive charge-discharge cycling throughout the cycle lifeof the rechargeable battery; and at least one polyolefinic microporouslayer wherein the polyolefinic microporous layer comprises apolyolefinic membrane of at least one of polyethylene or polypropyleneand is adapted to shut down and block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer wherein the ceramic composite layer includes a mixture ofheat-resistant particles and a high-temperature shutdown agent in amatrix material or a polymeric binder and wherein the ceramic compositelayer is adapted to at least block dendrite growth after repetitivecharge-discharge cycling and to prevent electronic shorting; and atleast one polyolefinic microporous layer wherein the layer is adapted toblock ionic flow between an anode and a cathode; or the separatorcomprises at least one ceramic composite layer wherein the ceramiccomposite layer is a coating with a thickness in the range of about 0.01to 25 microns and comprises: a mixture of heat-resistant particleshaving an average particle size in the range of 0.001 to 24 microns anda high-temperature shutdown agent in a matrix material or a polymericbinder, and said matrix material comprises polyethylene oxide (PEO),polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE),polyurethane, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA),polytetraethylene glycol diacrylate, copolymers thereof, or mixturesthereof, wherein the heat-resistant particles comprise silicon dioxide(SiO₂), aluminum oxide (Al₂O₃), calcium carbonate (CaCO₃), titaniumdioxide (TiO₂), SiS₂, SiPO₄, or mixtures thereof, and wherein theceramic composite layer is adapted to at least block dendrite growthafter repetitive charge-discharge cycling and thereby to preventelectronic shorting by preventing direct contact between an anode and acathode throughout repetitive charge-discharge cycling throughout thecycle life of the battery; and at least one polyolefinic microporouslayer wherein the polyolefinic microporous layer comprises a shutdownpolyolefinic membrane of polyethylene or polypropylene and is adapted toblock ionic flow between the anode and the cathode; or the separatorcomprises at least one ceramic composite layer wherein the ceramiccomposite layer is a coating with a thickness in the range of about 0.01to 25 microns and comprises: a mixture of heat-resisitant particleshaving an average particle size in the range of 0.001 to 24 microns anda high-temperature shutdown agent in a polymer matrix material or apolymeric binder, wherein the polymer matrix material comprises PVDF(polyvinylidene fluoride), PAN (polyacrylonitrile), PEO (polyethyleneoxide), or copolymers or mixtures thereof, and wherein the ceramiccomposite layer is adapted to at least block dendrite growth afterrepetitive charge-discharge cycling and to prevent electronic shortingthroughout repetitive charge-discharge cycling throughout the cycle lifeof the rechargeable battery; and at least one polyolefinic microporouslayer wherein the polyolefinic microporous layer comprises apolyolefinic membrane of at least one of polyethylene or polypropyleneand is adapted to shut down and block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer, said layer being formed from a coating composition which includesa matrix material or a polymeric binder; heat-resistant particles; and alow-temperature shutdown agent; said layer being adapted to at leastblock dendrite growth and to prevent electronic shorting; and at leastone polyolefinic microporous layer, said layer being adapted to blockionic flow between an anode and a cathode; or the separator comprises atleast one ceramic composite layer wherein the ceramic composite layer isa coating with a thickness in the range of about 0.01 to 25 microns andcomprises: a mixture of heat-resistant particles having an averageparticle size in the range of 0.001 to 24 microns and a low-temperatureshutdown agent in a polymer matrix material or a polymeric binder,wherein the heat-resistant particles comprise silicon dioxide (SiO₂),aluminum oxide (Al₂O₃), calcium carbonate (CaCO₃), titanium dioxide(TiO₂), SiS₂, SiPO₄, or mixtures thereof, and wherein the ceramiccomposite layer is adapted to at least block dendrite growth afterrepetitive charge-discharge cycling and to prevent electronic shortingthroughout repetitive charge-dischargecycling throughout the cycle lifeof the rechargeable battery; and at least one polyolefinic microporouslayer wherein the polyolefinic microporous layer comprises apolyolefinic membrane of at least one of polyethylene or polypropyleneand is adapted to shut down and block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer, wherein the ceramic composite layer comprises: a mixture of about20-95% by weight of heat-resistant particles, about 5-80% by weight of amatrix material or a polymeric binder; and a low-temperature shutdownagent, wherein the ceramic composite layer is adapted to at least blockdendrite growth after repetitive charge-discharge cycling and thereby toprevent electronic shorting; and at least one polyolefinic microporouslayer having a porosity in the range of about 20-80%, an average poresize in the range of about 0.02 to 2 microns, and wherein thepolyolefinic microporous layer is adapted to block ionic flow between ananode and a cathode; or the separator comprises at least one ceramiccomposite layer wherein the ceramic composite layer is a coating with athickness in the range of about 0.01 to 25 microns and comprises: amixture of heat-resistant particles having an average particle size inthe range of 0.001 to 24 microns and a low-temperature shutdown agent ina matrix material or a polymeric binder, the said matrix materialcomprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF),polytetrafluoroethylene (PTFE), polyurethane, polyacrylonitrile (PAN),polymethylmethacrylate (PMMA), polytetraethylene glycol diacrylate,copolymers thereof, or mixtures thereof, wherein the heat-resistantparticles comprise silicon dioxide (SiO₂), aluminum oxide (Al₂O₃),calcium carbonate (CaCO₃), titanium dioxide (TiO₂), SiS₂, SiPO₄, andwherein the ceramic composite layer is adapted to at least blockdendrite growth after repetitive charge-discharge cycling and thereby toprevent electronic shorting by preventing direct contact between ananode and a cathode throughout repetitive charge-discharge cyclingthroughout the cycle life of the battery; and at least one polyolefinicmicroporous layer wherein the polyolefinic microporous layer comprises ashutdown polyolefinic membrane of polyethylene or polypropylene and isadapted to block ionic flow between the anode and the cathode; or theseparator comprises at least one ceramic composite layer wherein theceramic composite layer is a coating with a thickness in the range ofabout 0.01 to 25 microns and comprises: a mixture of heat-resistantparticles having an average particle size in the range of 0.001 to 24microns and a low-temperature shutdown agent in a polymer matrixmaterial or a polymeric binder, wherein the polymer matrix materialcomprises PVDF (polyvinylidene fluoride), PAN (polyacrylonitrile), PEO(polyethylene oxide), or copolymers or mixtures thereof, and wherein theceramic composite layer is adapted to at least block dendrite growthafter repetitive charge-discharge cycling and to prevent electronicshorting throughout repetitive charge-dischargecycling throughout thecycle life of the rechargeable battery; and at least one polyolefinicmicroporous layer wherein the polyolefinic microporous layer comprises apolyolefinic membrane of at least one of polyethylene or polypropyleneand is adapted to shut down and block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer, said layer being formed from a coating composition which includesa matrix material or a polymeric binder; heat-resistant particles; and athickener and/or a X-Ray detectable agent, element or material; saidlayer being adapted to at least block dendrite growth and to preventelectronic shorting; and at least one polyolefinic microporous layer,said layer being adapted to block ionic flow between an anode and acathode; or the separator comprises at least one ceramic composite layerwherein the ceramic composite layer is a coating with a thickness in therange of about 0.01 to 25 microns and comprises: a mixture ofheat-resistant particles having an average particle size in the range of0.001 to 24 microns and a low-temperature shutdown agent in a polymermatrix material or a polymeric binder, wherein the heat-resistantparticles comprise silicon dioxide (SiO₂), aluminum oxide (Al₂O₃),calcium carbonate (CaCO₃), titanium dioxide (TiO₂), SiS₂, SiPO₄, ormixtures thereof, and wherein the ceramic composite layer is adapted toat least block dendrite growth after repetitive charge-discharge cyclingand to prevent electronic shorting throughout repetitivecharge-dischargecycling throughout the cycle life of the rechargeablebattery; and at least one polyolefinic microporous layer wherein thepolyolefinic microporous layer comprises a polyolefinic membrane of atleast one of polyethylene or polypropylene and is adapted to shut downand block ionic flow between the anode and the cathode; or the separatorcomprises at least one ceramic composite layer, wherein the ceramiccomposite layer comprises: a mixture of about 20-95% by weight ofheat-resistant particles, about 5-80% by weight of a matrix material ora polymeric binder; and a thickener and/or X-Ray detectable agent,wherein the ceramic composite layer is adapted to at least blockdendrite growth after repetitive charge-discharge cycling and thereby toprevent electronic shorting; and at least one polyolefinic microporouslayer having a porosity in the range of about 20-80%, an average poresize in the range of about 0.02 to 2 microns, and wherein thepolyolefinic microporous layer is adapted to block ionic flow between ananode and a cathode; or the separator comprises at least one ceramiccomposite layer wherein the ceramic composite layer is a coating with athickness in the range of about 0.01 to 25 microns and comprises: amixture of heat-resistant particles having an average particle size inthe range of 0.001 to 24 microns and a thickener and/or X-Ray detectableagent in a matrix material or a polymeric binder, the said matrixmaterial comprises polyethylene oxide (PEO), polyvinylidene fluoride(PVDF), polytetrafluoroethylene (PTFE), polyurethane, polyacrylonitrile(PAN), polymethylmethacrylate (PMMA), polytetraethylene glycoldiacrylate, copolymers thereof, or mixtures thereof, wherein theheat-resistant particles comprise silicon dioxide (SiO₂), aluminum oxide(Al₂O₃), calcium carbonate (CaCO₃), titanium dioxide (TiO₂), SiS₂,SiPO₄, and wherein the ceramic composite layer is adapted to at leastblock dendrite growth after repetitive charge-discharge cycling andthereby to prevent electronic shorting by preventing direct contactbetween an anode and a cathode throughout repetitive charge-dischargecycling throughout the cycle life of the battery; and at least onepolyolefinic microporous layer wherein the polyolefinic microporouslayer comprises a shutdown polyolefinic membrane of polyethylene orpolypropylene and is adapted to block ionic flow between the anode andthe cathode; or the separator comprises at least one ceramic compositelayer wherein the ceramic composite layer is a coating with a thicknessin the range of about 0.01 to 25 microns and comprises: a mixture ofheat-resistant particles having an average particle size in the range of0.001 to 24 microns and a thickener and/or X-Ray detectable agent in apolymer matrix material or a polymeric binder, wherein the polymermatrix material comprises PVDF (polyvinylidene fluoride), PAN(polyacrylonitrile), PEO (polyethylene oxide), or copolymers or mixturesthereof, and wherein the ceramic composite layer is adapted to at leastblock dendrite growth after repetitive charge-discharge cycling and toprevent electronic shorting throughout repetitivecharge-dischargecycling throughout the cycle life of the rechargeablebattery; and at least one polyolefinic microporous layer wherein thepolyolefinic microporous layer comprises a polyolefinic membrane of atleast one of polyethylene or polypropylene and is adapted to shut downand block ionic flow between the anode and the cathode.
 975. A separatorfor an energy storage system, wherein the separator comprise at leastone ceramic composite layer or coating, said layer including a mixtureof 20-95% by weight of heat-resistant particles selected from the groupconsisting of SiO₂, Al₂O₃, CaCO₃, TiO₂, SiS₂, SiPO₄ and the like, andmixtures thereof; 5-80% by weight of a matrix material or a polymericbinder, said matrix material being selected from the group consisting ofpolyethylene oxide, polyvinylidene fluoride, polytetrafluoroethylene,copolymers of the foregoing, and mixtures thereof; and an adhesionagent, said layer being adapted to at least block dendrite growth and toprevent electronic shorting; and at least one polyolefinic microporouslayer having a porosity in the range of 20-80%, an average pore size inthe range of 0.02 to 2 microns, and a Gurley Number in the range of 15to 150 sec, said layer being adapted to block ionic flow between ananode and a cathode; or the separator comprises at least one ceramiccomposite layer or coating, said layer including a mixture of 20-95% byweight of heat-resistant particles selected from the group consisting ofSiO₂, Al₂O₃, CaCO₃, TiO₂, SiS₂, SiPO₄ and the like, and mixturesthereof; 5-80% by weight of a matrix material or a polymeric binder,said matrix material being selected from the group consisting ofpolyethylene oxide, polyvinylidene fluoride, polytetrafluoroethylene,copolymers of the foregoing, and mixtures thereof; and a frictionreducing agent, said layer being adapted to at least block dendritegrowth and to prevent electronic shorting; and at least one polyolefinicmicroporous layer having a porosity in the range of 20-80%, an averagepore size in the range of 0.02 to 2 microns, and a Gurley Number in therange of 15 to 150 sec, said layer being adapted to block ionic flowbetween an anode and a cathode; or the separator comprises at least oneceramic composite layer or coating, said layer including a mixture of20-95% by weight of heat-resistant particles selected from the groupconsisting of SiO₂, Al₂O₃, CaCO₃, TiO₂, SiS₂, SiPO₄ and the like, andmixtures thereof, and 5-80% by weight of a matrix material or apolymeric binder and a high-temperature shutdown agent, said matrixmaterial selected from the group consisting of polyethylene oxide,polyvinylidene fluoride, polytetrafluoroethylene, copolymers of theforegoing, and mixtures thereof, said layer being adapted to at leastblock dendrite growth and to prevent electronic shorting; and at leastone polyolefinic microporous layer having a porosity in the range of20-80%, an average pore size in the range of 0.02 to 2 microns, and aGurley Number in the range of 15 to 150 sec, said layer being adapted toblock ionicflow between an anode and a cathode; or the separatorcomprises at least one ceramic composite layer or coating, said layerincluding a mixture of 20-95% by weight of heat-resistant particlesselected from the group consisting of SiO₂, Al₂O₃, CaCO₃, TiO₂, SiS₂,SiPO₄ and the like, and mixtures thereof; 5-80% by weight of a matrixmaterial or a polymeric binder, said matrix material being selected fromthe group consisting of polyethylene oxide, polyvinylidene fluoride,polytetrafluoroethylene, copolymers of the foregoing, and mixturesthereof; and a low-temperature shutdown agent, said layer being adaptedto at least block dendrite growth and to prevent electronic shorting;and at least one polyolefinic microporous layer having a porosity in therange of 20-80%, an average pore size in the range of 0.02 to 2 microns,and a Gurley Number in the range of 15 to 150 sec, said layer beingadapted to block ionic flow between an anode and a cathode; or theseparator comprises at least one ceramic composite layer wherein theceramic composite layer includes a mixture of heat-resistant particlesand a low-temperature shutdown agent in a matrix material or a polymericbinder, and wherein the ceramic composite layer is adapted to at leastblock dendrite growth after repetitive charge-discharge cycling and toprevent electronic shorting; and at least one polyolefinic microporouslayer wherein the layer is adapted to block ionic flow between an anodeand a cathode; or the separator comprises at least one ceramic compositelayer or coating, said layer including a mixture of 20-95% by weight ofheat-resistant particles selected from the group consisting of SiO₂,Al₂O₃, CaCO₃, TiO₂, SiS₂, SiPO₄ and the like, and mixtures thereof;5-80% by weight of a matrix material or a polymeric binder, said matrixmaterial being selected from the group consisting of polyethylene oxide,polyvinylidene fluoride, polytetrafluoroethylene, copolymers of theforegoing, and mixtures thereof; and a low-temperature shutdown agent,said layer being adapted to at least block dendrite growth and toprevent electronic shorting; and at least one polyolefinic microporouslayer having a porosity in the range of 20-80%, an average pore size inthe range of 0.02 to 2 microns, and a Gurley Number in the range of 15to 150 sec, said layer being adapted to block ionic flow between ananode and a cathode.